Distillation Calculation for the Separation of {sup 13}CH{sub 4} from LNG

Energy Technology Data Exchange (ETDEWEB)

Song, K.M.; Son, S.H.; Kim, K.S.; Lee, S.K. [Korea Electric Power Research Institute, Taejon (Korea)

2002-07-01

For the purpose of {sup 13}CH{sub 4} production from LNG, the theoretical number of stages and the number of distillation column required for the separation of {sup 13}CH{sub 4} from {sup 12}CH{sub 4}/{sup 13}CH{sub 4} mixture of containing 1%-{sup 13}CH{sub 4} are calculated. Assuming the ideal liquid mixture of containing 1%-{sup 13}CH{sub 4} are calculated. Assuming the ideal liquid mixture of {sup 12}CH{sub 4} and {sup 13}CH{sub 4}, the theoretical number of stages are calculated by smoker equation and FUG method. Using the correlation between the minimum theoretical number of stages and the optimum theoretical number of stages, the number of distillation groups is calculated. From this calculation, we know that 6 groups of distillation tower with 600 stages per one column are needed for the production of 90%-{sup 13}CH{sub 4}. (author). 5 refs., 5 figs., 4 tabs.

CO2/CH4 Separation via Polymeric Blend Membrane

Directory of Open Access Journals (Sweden)

H. Sanaeepur

2013-01-01

Full Text Available CO2/CH4 gas separation is a very important applicatable process in upgrading the natural gas and landfil gas recovery. In this work, to investigate the membrane separation process performance, the gas permeation results andCO2/CH4 separation characteristics of different prepared membranes (via blending different molecular weights of polyethylene glycol (PEG as a modifier with acrylonitrile-butadiene-styrene (ABS as a backbone structure have been studied. Furthermore, SEM analysis was carried out for morphological investigations. The effect of PEG content on gas transport properties on the selected sample was also studied. The effect of pressure on CO2 permeation was examined and showed that at the pressure beyond 4 bar, permeability is not affected by pressure. The results showed that more or less in all cases, incorporation of PEG molecules without any significant increase in CH4 permeability increases the CO2/CH4 selectivity. From the view point of gas separation applications the resultant data are within commercial attractive range

Replacement of CH4 in the hydrate by use of liquid CO2

International Nuclear Information System (INIS)

Ota, Masaki; Morohashi, Kenji; Abe, Yuki; Watanabe, Masaru; Smith, Richard Lee Jr.; Inomata, Hiroshi

2005-01-01

The dynamics of CH 4 replacement in the CH 4 hydrate with saturated liquid CO 2 at 273.2 K was measured with a high pressure optical cell. The results showed that CH 4 in the hydrate gradually moved to the liquid CO 2 phase while CO 2 in the liquid phase penetrated into the hydrate from the quantitative analysis. The decomposing process of the CH 4 hydrate during the replacement was analyzed with in situ Raman spectroscopy, which allowed us to distinguish the cage structure of the CH 4 hydrate and discuss the microscopic view of the replacement in the hydrate. It was found that the decomposition of the medium cage (M-cage) in the CH 4 hydrate proceeded faster than that of the small cage (S-cage). The observed rate difference could be related to the stability of the S-cage in the CH 4 hydrate or the re-formation tendency of CH 4 and water molecules in the S-cage after decomposing the hydrate structure, whereas the guest molecule exchange of CH 4 with CO 2 could occur in the M-cage. Based on the experimental data, we developed a kinetic model for calculation of the CH 4 remaining in the hydrate considering the decomposition rate difference between the M-cage and S-cage in the CH 4 hydrate. The results indicate that the driving force could be the fugacity difference between the fluid phase and the hydrate phase for the replacement process

Methane (CH4) Flux for North America L4 Daily V1 (CMS_CH4_FLX_NAD) at GES DISC

Data.gov (United States)

National Aeronautics and Space Administration — The CMS Methane (CH4) Flux for North America data set contains estimates of methane emission in North America based on an inversion of the GEOS-Chem chemical...

On the feasibility of chemi-ion formation in the system CH2CH(ã 4A″)+O(3P)

Science.gov (United States)

Metropoulos, Aristophanes

2003-12-01

We have investigated theoretically the possibility that the CH2CH(ã 4A″) radical can generate the CH2CHO+(X1A') ion upon collisions with O(3P). We have concluded that this is very unlikely because the minimum of the ground-state potential-energy surface of the ion is at about the same level as the potential energy of the asymptotic CH2CH(ã 4A″)+O(3P) fragments. In addition the Franck-Condon factors should not be favorable because of a drastic change in the geometry of the ion.

China’s regional CH_4 emissions: Characteristics, interregional transfer and mitigation policies

International Nuclear Information System (INIS)

Zhang, Bo; Yang, T.R.; Chen, B.; Sun, X.D.

2016-01-01

Highlights: • China’s CH_4 emissions have significant contributions to global climate change. • The total CH_4 emissions in 2010 amount to 44.3 Tg, half from energy activities. • Half of the national total direct emissions are embodied in interregional trade. • 2/3 of the embodied emission transfers via domestic trade are energy-related. • A national comprehensive action plan to reduce CH_4 emissions should be designed. - Abstract: Methane (CH_4), the second largest greenhouse gas emitted in China, hasn’t been given enough attention in the country’s policies and actions for addressing climate change. This paper aims to perform a bottom-up estimation and multi-regional input–output analysis for China’s anthropogenic CH_4 emissions from both production-based and consumption-based insights. As the world’s largest CH_4 emitter, China’s total anthropogenic CH_4 emissions in 2010 are estimated at 44.3 Tg and correspond to 1507.9 Mt CO_2-eq by the lower global warming potential factor of 34. Energy activities as the largest contributor hold about half of the national total emissions, mainly from coal mining. Inherent economic driving factors covering consumption, investment and international exports play an important role in determining regional CH_4 emission inventories. Interregional transfers of embodied emissions via domestic trade are equivalent to half of the national total emissions from domestic production, of which two thirds are energy-related embodied emissions. Most central and western regions as net interregional CH_4 exporters such as Shanxi and Inner Mongolia have higher direct emissions, while the eastern coastal regions as net interregional importers such as Guangdong and Jiangsu always have larger embodied emissions. Since China’s CH_4 emissions have significant contributions to global climate change, a national comprehensive action plan to reduce CH_4 emissions should be designed by considering supply-side and demand

Effect of CH4 concentration on the growth behavior, structure, and transparent properties of ultrananocrystalline diamond films synthesized by focused microwave Ar/CH4/H2 plasma jets

International Nuclear Information System (INIS)

Liao, Wen-Hsiang; Lin, Chii-Ruey; Wei, Da-Hua

2013-01-01

The effects of CH 4 concentration (0.5–5%) on the growth mechanisms, nanostructures, and optically transparent properties of ultrananocrystalline diamond (UNCD) films grown from focused microwave Ar/CH 4 /H 2 (argon-rich) plasma jets were systematically studied. The research results indicated that the grain size and surface roughness of the diamond films increased with increasing CH 4 concentration in the plasma jet, however, the nondiamond contents in films would not be correspondingly decreased resulting from the dispersed diamond nanocrystallites in the films synthesized at higher CH 4 concentration. The reason is due to that the relative emission intensity ratios of the C 2 /H α and the CH/C 2 in the plasma jets were increased and decreased with increasing CH 4 concentration, respectively, to lower the etching of nondiamond phase and the renucleation of diamond during synthesis. The studies of transmission electron microscopy demonstrated that, while the CH 4 introduction of 1% into the plasma jet produced the UNCD films with a spherical geometry (4–8 nm) and the CH 4 introduction of 5% into the plasma jet led to the elongated (∼90 nm in length and ∼35 nm in width) grains in the nanocrystalline diamond (NCD) films with a dendrite-like geometry. The transmittance of diamond films was decreased gradually by films transition from UNCD to NCD, resulting from the enhanced surface roughness and nondiamond contents in films to concurrently increase the light scattering and absorption during photon transmission.

Activation of sp3-CH Bonds in a Mono(pentamethylcyclopentadienyl)yttrium Complex. X-ray Crystal Structures and Dynamic Behavior of Cp*Y(o-C6H4CH2NMe2)2 and Cp*Y[o-C6H4CH2NMe(CH2-μ)][μ-o-C6H4CH2NMe(CH2-μ)]YCp*[THF

NARCIS (Netherlands)

Booij, Martin; Kiers, Niklaas H.; Meetsma, Auke; Teuben, Jan H.; Smeets, Wilberth J.J.; Spek, Anthony L.

1989-01-01

Reaction of Y(o-C6H4CH2NMe2)3 (1) with Cp*H gives Cp*Y(o-C6H4CH2NMe2)2 (2), which crystallizes in the monoclinic space group P21/n (No. 14) with a = 18.607 (4) Å, b = 15.633 (3) Å, c = 8.861 (3) Å, β = 102.73 (3)°, and Z = 4. Least-squares refinement with 3006 independent reflections (F > 4.0σ(F))

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

Science.gov (United States)

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.

A combustion setup to precisely reference δ13C and δ2H isotope ratios of pure CH4 to produce isotope reference gases of δ13C-CH4 in synthetic air

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H. Schaefer

2012-09-01

Full Text Available Isotope records of atmospheric CH4 can be used to infer changes in the biogeochemistry of CH4. One factor currently limiting the quantitative interpretation of such changes are uncertainties in the isotope measurements stemming from the lack of a unique isotope reference gas, certified for δ13C-CH4 or δ2H-CH4. We present a method to produce isotope reference gases for CH4 in synthetic air that are precisely anchored to the VPDB and VSMOW scales and have δ13C-CH4 values typical for the modern and glacial atmosphere. We quantitatively combusted two pure CH4 gases from fossil and biogenic sources and determined the δ13C and δ2H values of the produced CO2 and H2O relative to the VPDB and VSMOW scales within a very small analytical uncertainty of 0.04‰ and 0.7‰, respectively. We found isotope ratios of −39.56‰ and −56.37‰ for δ13C and −170.1‰ and −317.4‰ for δ2H in the fossil and biogenic CH4, respectively. We used both CH4 types as parental gases from which we mixed two filial CH4 gases. Their δ13C was determined to be −42.21‰ and −47.25‰ representing glacial and present atmospheric δ13C-CH4. The δ2H isotope ratios of the filial CH4 gases were found to be −193.1‰ and −237.1‰, respectively. Next, we mixed aliquots of the filial CH4 gases with ultrapure N2/O2 (CH4 ≤ 2 ppb producing two isotope reference gases of synthetic air with CH4 mixing ratios near atmospheric values. We show that our method is reproducible and does not introduce isotopic fractionation for δ13C within the uncertainties of our detection limit (we cannot conclude this for δ2H because our system is currently not prepared for δ2H-CH4 measurements in air samples. The general principle of our method can be applied to produce synthetic isotope reference gases targeting δ2H-CH4 or other gas species.

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

Science.gov (United States)

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

Science.gov (United States)

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

Science.gov (United States)

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.

Macromolecule simulation and CH4 adsorption mechanism of coal vitrinite

Science.gov (United States)

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 graphene. However, the energy of the most preferential location is much lower than that of graphite/graphene. CH4 is more easily absorbed on the surface of vitrinite. Adsorbability varies considerably at different adsorption locations and sites on the surface of vitrinite. Crystal parameter of vitrinite is a = b = c = 15.8 Å and majority of its micropores are blow 15.8 Å, indicating that the vitrinite have the optimum adsorption aperture. It can explain its higher observed adsorption capacities for CH4 compared with graphite/graphene.

Evaluation of origins of CH4 carbon emitted from rice paddies

Science.gov (United States)

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.

CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4: Infrared spectra, radiative efficiencies, and global warming potentials

International Nuclear Information System (INIS)

Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

2016-01-01

Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600–3500 cm"−"1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm"−"1 molecule"−"1): CH_3Cl, 660–780 cm"−"1, (3.89±0.19)×10"−"1"8; CH_2Cl_2, 650–800 cm"−"1, (2.16±0.11)×10"−"1"7; CHCl_3, 720–810 cm"−"1, (4.08±0.20)×10"−"1"7; and CCl_4, 730–825 cm"−"1, (6.30±0.31)×10"−"1"7. CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons. - Highlights: • Infrared spectra reported for CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4. • REs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1, respectively. • GWPs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 5, 8, 15, and 1775, respectively.

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

Science.gov (United States)

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).

Assessing fugitive emissions of CH4 from high-pressure gas pipelines

Science.gov (United States)

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.

Vibrational transition moments of CH4 from first principles

Science.gov (United States)

Yurchenko, Sergei N.; Tennyson, Jonathan; Barber, Robert J.; Thiel, Walter

2013-09-01

New nine-dimensional (9D), ab initio electric dipole moment surfaces (DMSs) of methane in its ground electronic state are presented. The DMSs are computed using an explicitly correlated coupled cluster CCSD(T)-F12 method in conjunction with an F12-optimized correlation consistent basis set of the TZ-family. A symmetrized molecular bond representation is used to parameterise these 9D DMSs in terms of sixth-order polynomials. Vibrational transition moments as well as band intensities for a large number of IR-active vibrational bands of 12CH4 are computed by vibrationally averaging the ab initio dipole moment components. The vibrational wavefunctions required for these averages are computed variationally using the program TROVE and a new ‘spectroscopic’ 12CH4 potential energy surface. The new DMSs will be used to produce a hot line list for 12CH4.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Unusually Warm Spring Temperatures Magnify Annual CH4 Losses From Arctic Ecosystems

Science.gov (United States)

Goodrich, J. P.; Oechel, W. C.; Gioli, B.; Murphy, P.; Zona, D.

2015-12-01

The relatively fast pace of Northern high latitude warming puts the very large permafrost soil C pool at a higher risk of being lost to the atmosphere as CH4. Estimates for the Arctic tundra's contribution to the global wetland CH4 emissions range from 15-27 TgCH4 y-1 (8-14% of total). However, these estimates are largely based on data from the growing season, or from boreal systems underlain by discontinuous permafrost with different physical, hydrological, and biogeochemical dynamics than continuous permafrost zones. Recent data from a transect of eddy covariance flux towers across the North Slope of Alaska revealed the importance of cold season emissions to the annual CH4 budget, which may not correlate with summer flux patterns. However, understanding of the controls and inter-annual variability in fluxes at these different sites is lacking. Here, we present data from ~3 years at 5 tundra ecosystems along this Arctic transect to show the influence of earlier and deeper spring active layer thaw on timing and magnitude of CH4 fluxes. This year's warm spring led to significantly greater thaw depths and lower water tables than the previous year. Substantial CH4 emissions in 2015 were recorded at the wettest sites >20 days earlier than in the more meteorologically normal previous year. Since the soil remained saturated despite a lowered water table, total spring CH4 emissions more than doubled at these wet sites. At the drier sites, soil moisture declined with water table during the warmer spring, resulting in similar emissions to the previous year. However, deeper thaw depths prolonged fall and early winter emissions during the 'zero-curtain' soil temperature freezing phase, particularly at the drier site. In general, warmer spring temperatures in the Arctic may result in large increases in early season CH4 losses at wet sites and prolonged steady losses at the upland sites, enhancing the feedback between changing climate and tundra CH4 emissions at all sites.

OH vibrational activation and decay dynamics of CH4-OH entrance channel complexes

International Nuclear Information System (INIS)

Wheeler, Martyn D.; Tsiouris, Maria; Lester, Marsha I.; Lendvay, Gyoergy

2000-01-01

Infrared spectroscopy has been utilized to examine the structure and vibrational decay dynamics of CH 4 -OH complexes that have been stabilized in the entrance channel to the CH 4 +OH hydrogen abstraction reaction. Rotationally resolved infrared spectra of the CH 4 -OH complexes have been obtained in the OH fundamental and overtone regions using an IR-UV (infrared-ultraviolet) double-resonance technique. Pure OH stretching bands have been identified at 3563.45(5) and 6961.98(4) cm-1 (origins), along with combination bands involving the simultaneous excitation of OH stretching and intermolecular bending motions. The infrared spectra exhibit extensive homogeneous broadening arising from the rapid decay of vibrationally activated CH 4 -OH complexes due to vibrational relaxation and/or reaction. Lifetimes of 38(5) and 25(3) ps for CH 4 -OH prepared with one and two quanta of OH excitation, respectively, have been extracted from the infrared spectra. The nascent distribution of the OH products from vibrational predissociation has been evaluated by ultraviolet probe laser-induced fluorescence measurements. The dominant inelastic decay channel involves the transfer of one quantum of OH stretch to the pentad of CH 4 vibrational states with energies near 3000 cm-1. The experimental findings are compared with full collision studies of vibrationally excited OH with CH 4 . In addition, ab initio electronic structure calculations have been carried out to elucidate the minimum energy configuration of the CH 4 -OH complex. The calculations predict a C 3v geometry with the hydrogen of OH pointing toward one of four equivalent faces of the CH 4 tetrahedron, consistent with the analysis of the experimental infrared spectra. (c) 2000 American Institute of Physics

Effect of antisymmetric C–H stretching excitation on the dynamics of O({sup 1}D) + CH{sub 4} → OH + CH{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Pan, Huilin; Yang, Jiayue; Zhang, Dong; Shuai, Quan; Jiang, Bo [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Dai, Dongxu; Wu, Guorong, E-mail: wugr@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn; Yang, Xueming, E-mail: wugr@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

2014-04-21

The effect of antisymmetric C–H stretching excitation of CH{sub 4} on the dynamics and reactivity of the O({sup 1}D) + CH{sub 4} → OH + CD{sub 3} reaction at the collision energy of 6.10 kcal/mol has been investigated using the crossed-beam and time-sliced velocity map imaging techniques. The antisymmetric C–H stretching mode excited CH{sub 4} molecule was prepared by direct infrared excitation. From the measured images of the CH{sub 3} products with the infrared laser on and off, the product translational energy and angular distributions were derived for both the ground and vibrationally excited reactions. Experimental results show that the vibrational energy of the antisymmetric stretching excited CH{sub 4} reagent is channeled exclusively into the vibrational energy of the OH co-products and, hence, the OH products from the excited-state reaction are about one vibrational quantum hotter than those from the ground-state reaction, and the product angular distributions are barely affected by the vibrational excitation of the CH{sub 4} reagent. The reactivity was found to be suppressed by the antisymmetric stretching excitation of CH{sub 4} for all observed CH{sub 3} vibrational states. The degree of suppression is different for different CH{sub 3} vibrational states: the suppression is about 40%–60% for the ground state and the umbrella mode excited CH{sub 3} products, while for the CH{sub 3} products with one quantum symmetric stretching mode excitation, the suppression is much less pronounced. In consequence, the vibrational state distribution of the CH{sub 3} product from the excited-state reaction is considerably different from that of the ground-state reaction.

Influence of O_2 exposure on the interaction between CH_4 and amorphous AlYB_1_4

International Nuclear Information System (INIS)

Hunold, Oliver; Wiesing, Martin; Arcos, Teresa de los; Music, Denis; Grundmeier, Guido; Schneider, Jochen M.

2017-01-01

Highlights: • Influence of O_2 exposure on the surface chemistry of a-AlYB_1_4 on the interaction with CH_4 and PE studied by ab initio and UHV-AFM. • Predicted stronger interaction is consistent with experimentally observed trends. • Upon O_2 exposure surface bonding becomes more semiconducting causing a charge redistribution within the adsorbed CH_4 molecule. • The data serve as proof of concept for exploring polymer − hard coating interactions in varying atmospheres. - Abstract: The influence of surface oxidation on the interaction between CH_4 and amorphous AlYB_1_4 (a-AlYB_1_4) has been studied theoretically by using density functional theory and experimentally by ultra-high vacuum atomic force microscopy (UHV-AFM). CH_4 mimics the –CH_3 termination and aliphatic subunits of a polymer chain. Low-energy ion scattering measurements of magnetron sputtered thin films suggest that the bonding at the surfaces of pristine a-AlYB_1_4 and O_2 exposed a-AlYB_1_4 (O_2//a-AlYB_1_4) is metal-boron and metal-oxygen dominated, respectively. Based on the ab initio calculations the adsorption energies of CH_4 on a-AlYB_1_4 and O_2//a-AlYB_1_4 decreases from −0.07 to −0.30 eV, respectively. This trend is consistent with experimental data obtained by colloidal probe UHV-AFM studies with a polyethylene sphere, where larger adhesion forces for the O_2 exposed surface as compared to the pristine a-AlYB_1_4 surface were measured. No charge transfer takes place between CH_4 and the pristine as well as the O_2 exposed a-AlYB_1_4. Oxygen chemisorption induces changes in surface bonding. States at the Fermi level are depleted upon oxidation, hence the surface bonding becomes more semiconducting causing a charge redistribution within the adsorbed CH_4 molecule. Hence, these data serve as proof of concept for exploring the effect of O_2 exposure on the interaction between aliphatic polymers and a-AlYB_1_4 using a correlative experimental and theoretical research approach.

RELATIONSHIP BETWEEN ATMOSPHERIC CO_2 AND CH_4 CONCENTRATIONS AT SYOWA STATION, ANTARCTICA

OpenAIRE

アオキ, シュウジ; ナカザワ, タカキヨ; ムラヤマ, ショウヘイ; シミズ, アキラ; ハヤシ, マサヒコ; イワイ, クニモト; Shuhji, AOKI; Takakiyo, NAKAZAWA; Shohei, MURAYAMA; Akira, SHIMIZU; Masahiko, HAYASHI; Kunimoto, IWAI

1994-01-01

Precise measurements of the atmospheric CO_2 and CH_4 concentrations have been continued at Syowa Station since 1984 and 1987,respectively. Measured concentrations show secular increase, together with seasonal cycle and irregular variations. Negative correlation is clearly seen between the secular trends of the CO_2 and CH_4 concentrations. The increase rates of CO_2 and CH_4 show oscillations with periods of 2.3 to 2.8 years. The phases of the average seasonal cycles of CO_2 and CH_4 coincid...

Reticular synthesis of HKUST-like tbo MOFs with enhanced CH4 storage

KAUST Repository

Spanopoulos, Ioannis

2015-12-22

Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing MOFs for CH4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m2 g-1 and 2363 m2 cm-3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm3 (STP) g-1 and 221 cm3 (STP) cm-3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm3 (STP) g-1 and 175 cm3 (STP) cm-3 and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature (e.g. 326 cm3 (STP) g-1 and 194 cm3 (STP) cm-3 at 258 K). To better understand the structure-property relationship and gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites at the vicinity of the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars.

Reticular synthesis of HKUST-like tbo MOFs with enhanced CH4 storage

KAUST Repository

Spanopoulos, Ioannis; Tsangarakis, Constantinos; Klontzas, Emmanuel; Tylianakis, Emmanuel; Froudakis, George; Adil, Karim; Belmabkhout, Youssef; Eddaoudi, Mohamed; Trikalitis, Pantelis N.

2015-01-01

Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing MOFs for CH4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m2 g-1 and 2363 m2 cm-3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm3 (STP) g-1 and 221 cm3 (STP) cm-3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm3 (STP) g-1 and 175 cm3 (STP) cm-3 and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature (e.g. 326 cm3 (STP) g-1 and 194 cm3 (STP) cm-3 at 258 K). To better understand the structure-property relationship and gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites at the vicinity of the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars.

Assessing diel variation of CH4 flux from rice paddies through temperature patterns

Science.gov (United States)

Centeno, Caesar Arloo R.; Alberto, Ma Carmelita R.; Wassmann, Reiner; Sander, Bjoern Ole

2017-10-01

The diel variation in methane (CH4) flux from irrigated rice was characterized during the dry and wet cropping seasons in 2013 and 2014 using the eddy covariance (EC) technique. The EC technique has the advantage of obtaining measurements of fluxes at an extremely high temporal resolution (10Hz), meaning it records 36,000 measurements per hour. The EC measurements can very well capture the temporal variations of the diel (both diurnal and nocturnal) fluxes of CH4 and the environmental factors (temperature, surface energy flux, and gross ecosystem photosynthesis) at 30-min intervals. The information generated by this technique is important to enhance our mechanistic understanding of the different factors affecting the landscape scale diel CH4 flux. Distinct diel patterns of CH4 flux were observed when the data were partitioned into different cropping periods (pre-planting, growth, and fallow). The temporal variations of the diel CH4 flux during the dry seasons were more pronounced than during the wet seasons because the latter had so much climatic disturbance from heavy monsoon rains and occasional typhoons. Pearson correlation analysis and Granger causality test were used to confirm if the environmental factors evaluated were not only correlated with but also Granger-causing the diel CH4 flux. Soil temperature at 2.5 cm depth (Ts 2.5 cm) can be used as simple proxy for predicting diel variations of CH4 fluxes in rice paddies using simple linear regression during both the dry and wet seasons. This simple site-specific temperature response function can be used for gap-filling CH4 flux data for improving the estimates of CH4 source strength from irrigated rice production.

Annual variation of CH4 emissions from the middle taiga in West Siberian Lowland (2005–2009: a case of high CH4 flux and precipitation rate in the summer of 2007

Directory of Open Access Journals (Sweden)

M. Sasakawa

2012-03-01

Full Text Available We described continuous measurements of CH4 and CO2 concentration obtained at two sites placed in the middle taiga, Karasevoe (KRS and Demyanskoe (DEM, in West Siberian Lowland (WSL from 2005 to 2009. Although both CH4 and CO2 accumulation (ΔCH4 and ▵CO2 during night-time at KRS in June and July 2007 showed an anomalously high concentration, higher ratios of ΔCH4/ΔCO2 compared with those in other years indicated that a considerably higher CH4 flux occurred relative to the CO2 flux. The daily CH4 flux calculated with the ratio of ΔCH4/ΔCO2 and terrestrial biosphere CO2 flux from an ecosystem model showed a maximum in July at the both sites. Although anomalously high flux was observed in June and July 2007 at KRS, only a small flux variation was observed at DEM. The high regional CH4 flux in June and July 2007 at KRS was reproduced using a process-based ecosystem model, Vegetation Integrative Simulator for Trace gases (VISIT, in response to high water table depth caused by the anomalously high precipitation during the summer of 2007.

CH4 emissions from enteric fermentation in Austria

International Nuclear Information System (INIS)

Gebetsroither, E.; Orthofer, R.; Strebl, F.

2002-07-01

This report contains the results of an inventory for methane (CH 4 ) emissions from agricultural enteric fermentation in Austria for the period 1980-2001. Emissions were calculated according to IPCC guidelines. The detailed IPCC 'Tier 2' methodology was applied for cattle (which contribute the vast majority of emissions). The 'Tier 2' methodology relies on specific emission factors that are calculated from the energy intake for different cattle farming practices. The less detailed 'Tier 1' methodology was applied for all other animal categories. Emissions from organic and conventional farming practices were calculated separately. Results indicate that CH 4 emissions from manure management have increased from 1980 to a peak in 1984-1985, and since then have steadily declined. CH 4 emissions were about 169.300 t/yr in 'Kyoto' base year 1990 and have since declined by about 11 % to about 150.000 t/yr in 2001. Almost all emissions (95 % in 1990 and 94 % in 2001) are caused by cattle farming. The contribution of 'dairy cattle' to all emissions from cattle was 49 % in 1990, and has declined to 43 % in 2001. The overall reduction was caused mainly by a decrease in the total numbers of animals. However, in the case of dairy cows the reduction of animals is partly counterbalanced by an increase in emissions per animal (because of the increasing gross energy intake and milk production of milk cattle since 1990). Uncertainties of emissions were estimated with a 'Monte Carlo' simulation. Assuming a normal probability distribution, the calculated standard deviation is 4 %. This indicates there is a 95 % probability that CH 4 emissions are between ± 2 standard deviations, i.e. between 153.000 t and 178.000 t in the year 1990 and between 138.000 t and 162.000 t in the year 2001. (author)

Effects of plant species on soil microbial processes and CH4 emission from constructed wetlands

International Nuclear Information System (INIS)

Wang, Yanhua; Yang, Hao; Ye, Chun; Chen, Xia; Xie, Biao; Huang, Changchun; Zhang, Jixiang; Xu, Meina

2013-01-01

Methane (CH 4 ) emission from constructed wetland has raised environmental concern. This study evaluated the influence of mono and polyculture constructed wetland and seasonal variation on CH 4 fluxes. Methane emission data showed large temporal variation ranging from 0 to 249.29 mg CH 4 m −2 h −1 . Results indicated that the highest CH 4 flux was obtained in the polyculture system, planted with Phragmites australis, Zizania latifolia and Typha latifolia, reflecting polyculture system could stimulate CH 4 emission. FISH analysis showed the higher amount of methanotrophs in the profile of Z. latifolia in both mono and polyculture systems. The highest methanogens amount and relatively lower methanotrophs amount in the profile of polyculture system were obtained. The results support the characteristics of CH 4 fluxes. The polyculture constructed wetland has the higher potential of global warming. -- Highlights: ► The polyculture constructed wetland has the higher contribution to CH 4 emission. ► The CH 4 –C conversion ranged from 0 to 3.7%. ► The Z. latifolia played important roles in methanotrophs growth and CH 4 consumption. ► Major influence of T-N, TOC and plant cover on CH 4 emission was obtained. -- The polyculture constructed wetland has the higher contribution to global warming

Effect of interannual variation in winter vertical mixing on CH4 dynamics in a subtropical reservoir

Science.gov (United States)

Itoh, Masayuki; Kobayashi, Yuki; Chen, Tzong-Yueh; Tokida, Takeshi; Fukui, Manabu; Kojima, Hisaya; Miki, Takeshi; Tayasu, Ichiro; Shiah, Fuh-Kwo; Okuda, Noboru

2015-07-01

Although freshwaters are considered to be substantial natural sources of atmospheric methane (CH4), in situ processes of CH4 production and consumption in freshwater ecosystems are poorly understood, especially in subtropical areas, leading to uncertainties in the estimation of global CH4 emissions. To improve our understanding of physical and biogeochemical factors affecting CH4 dynamics in subtropical lakes, we examined vertical and seasonal profiles of dissolved CH4 and its carbon isotope ratio (δ13C) and conducted incubation experiments to assess CH4 production and oxidation in the deep subtropical Fei-Tsui Reservoir (FTR; Taiwan). The mixing pattern of the FTR is essentially monomixis, but the intensity of winter vertical mixing changes with climatic conditions. In years with incomplete vertical mixing (does not reach the bottom) and subsequent strong thermal stratification resulting in profundal hypoxia, we observed increases in sedimentary CH4 production and thus profundal CH4 storage with the development of reducing conditions. In contrast, in years with strong winter vertical mixing to the bottom of the reservoir, CH4 production was suppressed under NO3--rich conditions, during which denitrifiers have the competitive advantage over methanogens. Diffusive emission from profundal CH4 storage appeared to be negligible due to the efficiency of CH4 oxidation during ascent through methane-oxidizing bacteria (MOB) activity. Most of the profundal CH4 was rapidly oxidized by MOB in both oxic and anoxic layers, as characterized by its carbon isotope signature. In contrast, aerobic CH4 production in the subsurface layer, which may be enhanced under high temperatures in summer, may account for a large portion of atmospheric CH4 emissions from this reservoir. Our CH4 profiling results provide valuable information for future studies predicting CH4 emissions from subtropical lakes with the progress of global warming.

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

Science.gov (United States)

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.

Landscape Controls of CH4 Fluxes in a Catchment of the Forest Tundra in Northern Siberia

Science.gov (United States)

Flessa, H.; Rodionov, A.; Guggenberger, G.; Fuchs, H.; Magdon, P.; Shibistova, O.; Zrazhevskaya, G.; Kasansky, O.; Blodau, C.

2007-12-01

Soils have the capacity to both produce and consume atmospheric methane. The direction and the size of net- CH4 exchange between soils and atmosphere is mainly controlled by the soil aeration, temperature and the amount of bioavailable organic matter. All these factors are strongly influenced by distribution and seasonal dynamics of permafrost. Thus, distribution of permafrost and the thickness of the active layer can exert strong influence on CH4 dynamics in artic and northern boreal ecosystems. We analyzed the spatial and temporal variability of net-CH4 exchange within a catchment located in the Siberian forest tundra at the eastern shore of the lower Yenissej River to constrain the current function of this region as a sink or source of atmospheric CH4 and to gain insight into the potential for climatic change to alter the rate and form of carbon cycling and CH4 fluxes in this region. Net-fluxes of CH4 were measured from July to November 2003 and from August 2006 to July 2007 on representative soils of the catchment (mineral soils with different thawing depth, soils of bog plateaux) and on a thermokarst pond. In addition, dissolved CH4 in the stream draining the catchment was determined. Field observations, classification of landscape structures from satellite images and flux measurements were combined to estimate total catchment CH4 exchange. Nearly all soils of the catchment were net-sinks of atmospheric CH4 with annual CH4-C uptake rates ranging between 1.2 and 0.2 kg ha-1 yr-1. The active layer depth was the main factor determining the size of CH4 uptake. Total net-exchange of CH4 from the catchment was dominated by ponds that covered only about 2% of the catchment area. Due to high CH4 emission from these aquatic systems, the catchment was a net source of atmospheric CH4 with a mean annual emission of approximately 170 kg CH4-C ha-1. CH4 concentration in streams draining the catchment can help to identify areas with high CH4 production. The results suggest

A Monte Carlo study of backscattering effects in the photoelectron emission from CsI into CH$_{4}$ and Ar-CH$_{4}$ mixtures

CERN Document Server

Escada, J; Rachinhas, P J B M; Lopes, J A M; Santos, F P; Távora, L M N; Conde, C A N; Stauffer, A D

2007-01-01

Monte Carlo simulation is used to investigate photoelectron backscattering effects in the emission from a CsI photocathode into CH4 and Ar-CH4 mixtures for incident monochromatic photons with energies Eph in the range 6.8 eV to 9.8 eV (182 nm to 127 nm), and photons from a continuous VUV Hg(Ar) lamp with a spectral distribution peaked at Eph = 6.7 eV (185 nm), considering reduced applied electric fields E/N in the 0.1 Td to 40 Td range. The addition of CH4 to a noble gas efficiently increases electron transmission and drift velocity, due to vibrational excitation of the molecules at low electron energies. Results are presented for the photoelectron transmission efficiencies f, where f is the fraction of the number of photoelectrons emitted from CsI which are transmitted through the gas as compared to vacuum. The dependence of f on Eph, E/N, and mixture composition is analyzed and explained in terms of electron scattering in the different gas media, and results are compared with available measurements. Electro...

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Macromolecule simulation and CH{sub 4} adsorption mechanism of coal vitrinite

Energy Technology Data Exchange (ETDEWEB)

Yu, Song, E-mail: songyu10094488@126.com [School of Resources and Earth Science, China University of Mining & Technology, Xuzhou 221116 (China); Key Laboratory of Coal bed Methane Resource & Reservoir Formation Process, Ministry of Education, Xuzhou 221008 (China); Yan-ming, Zhu; Wu, Li [School of Resources and Earth Science, China University of Mining & Technology, Xuzhou 221116 (China); Key Laboratory of Coal bed Methane Resource & Reservoir Formation Process, Ministry of Education, Xuzhou 221008 (China)

2017-02-28

Highlights: • Molecular model of single maceral vitrinite was obtained by {sup 13}C NMR, FT IR and HRTEM. • An optimal configuration was obtained through calculation of MM and MD. • The adsorption parameters for methane and vitrinite were determined with DFT and GCMC. - Abstract: The microscopic mechanism of interactions between CH{sub 4} 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, {sup 13}C 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 CH{sub 4} is conducted. A saturated state is reached after absorbing 17 CH{sub 4}s per coal vitrinite molecule. CH{sub 4} 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 [−C=O] and [C−O−C]. CH{sub 4} 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 [−C=O] (1.64 Å) < [C−O−C] (1.89 Å) < [−COOH] (3.78 Å) < [-CH{sub 3}] (4.11 Å) according to the average RDF curves. CH{sub 4} enriches

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

Science.gov (United States)

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.

Microbial CH4 and N2O consumption in acidic wetlands

Directory of Open Access Journals (Sweden)

Steffen eKolb

2012-03-01

Full Text Available 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 dentrifiers that consume atmospheric CH4 and N2O in acidic wetlands.

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH)

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, M. D.

2005-01-01

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy...

Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H + CH(4) H(2) + CH(3).

Science.gov (United States)

Banks, Simon T; Clary, David C

2009-01-14

We consider the general problem of vibrational analysis at nonglobally optimized points on a reduced dimensional reaction surface. We discuss the importance of the use of curvilinear internal coordinates to describe molecular motion and derive a curvilinear projection operator to remove the contribution of nonzero gradients from the Hessian matrix. Our projection scheme is tested in the context of a two-dimensional quantum scattering calculation for the reaction H + CH(4) --> H(2) + CH(3) and its reverse H(2) + CH(3) --> H + CH(4). Using zero-point energies calculated via rectilinear and curvilinear projections we construct two two-dimensional, adiabatically corrected, ab initio reaction surfaces for this system. It is shown that the use of curvilinear coordinates removes unphysical imaginary frequencies observed with rectilinear projection and leads to significantly improved thermal rate constants for both the forward and reverse reactions.

Study on the Promotion Effect of Ionic Liquid on CH4 Hydrate Formation

International Nuclear Information System (INIS)

Shin, Ju-Young; Mun, Sungyong; Kang, Seong-Pil; Kim, Kisub

2013-01-01

In this study, we investigated the kinetics of gas hydrate formation in the presence of ionic liquid (IL). Hydroxyethyl-methyl-morpholinium chloride (HEMM-Cl) was chosen as a material for the promotion effect test. Phase equilibrium curve for CH 4 hydrate with aqueous IL solution was obtained and its induction time and consumed amount of CH 4 gas were also measured. Aqueous solutions containing 20-20,000 ppm of HEMM-Cl was prepared and studied at 70 bar and 274.15 K. To compare the measured results to those of the conventional promoter, sodium dodecyl sulfate was also tested at the same condition. Result showed that the hydrate equilibrium curve was shifted toward higher pressure and lower temperature region. In addition, the induction time on CH 4 hydrate formation in the presence of IL was not shown. The amount of consumed CH 4 was increased with the whole range of tested concentration of IL and the highest consumption of CH 4 happened at 1,000 ppm of HEMM-Cl. HEMM-Cl induced and enhanced the CH 4 hydrate formation with a small amount of addition. Obtained result is expected to be applied for the development of technologies such as gas storage and transport using gas hydrates

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

Directory of Open Access Journals (Sweden)

Kurt Spokas

2015-06-01

Full Text Available Abstract Improved quantification of diverse CH4 sources at the urban scale is needed to guide local 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 landfill CH4 generation (methanogenesis, but does not explicitly consider climate or soil dependencies for emissions. Relying on a comprehensive California landfill database, a field-validated process-based model for landfill CH4 emissions (CALMIM, and select field measurements at 10 California sites with a variety of methods, we support the contrary position: Limited climate dependency for methanogenesis, but strong climate dependency for landfill CH4 emissions. Contrary to the historic IPCC empirical model for methanogenesis with kinetic constants related to climate, we demonstrate a simpler and more robust linear empirical relationship (r2 = 0.85; n=128 between waste mass and landfill biogas recovery [126 × 10-6 Nm3 CH4 hr-1 Mgwaste-1]. More interestingly, there are no statistically significant relationships with climate, site age, or status (open/closed for landfill biogas recovery. The current IPCC methodology does not consider soil or climate drivers for gaseous transport or seasonal methanotrophy in different cover soils. On the other hand, we illustrate strong climate and soil dependencies for landfill emissions—e.g., average intermediate cover emissions below 20 g CH4 m-2 d-1 when the site’s mean annual precipitation is >500 mm y-1. Thereby, for the California landfill CH4 inventory, the highest-emitting sites shift from landfills containing the largest mass of waste to sites dominated by intermediate cover types having a reduced rate of soil CH4 oxidation during the annual cycle. These differences have profound implications for developing more realistic, science-based urban and regional scale GHG inventories for landfill CH4 while reducing

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

Science.gov (United States)

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

Science.gov (United States)

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.

Surface study of platinum decorated graphene towards adsorption of NH_3 and CH_4

International Nuclear Information System (INIS)

Rad, Ali Shokuhi; Pazoki, Hossein; Mohseni, Soheil; Zareyee, Daryoush; Peyravi, Majid

2016-01-01

To distinguish the potential of graphene sensors, there is a need to recognize the interaction between graphene sheet and adsorbing molecules. We used density functional theory (DFT) calculations to study the properties of pristine as well as Pt-decorated graphene sheet upon adsorption of NH_3 and CH_4 on its surface to exploit its potential to be as gas sensors for them. We found much higher adsorption, higher charge transfer, lower intermolecular distance, and higher orbital hybridizing upon adsorption of NH_3 and CH_4 gas molecules on Pt-decorated graphene compared to pristine graphene. Also our calculations reveal that the adsorption energies on Pt-decorated graphene sheet are in order of NH_3 >CH_4 which could be corresponded to the order of their sensitivity on this modified surface. We used orbital analysis including density of states as well as frontier molecular orbital study for all analyte-surface systems to more understanding the kind of interaction (physisorption or chemisorption). Consequently, the Pt-decorated graphene can transform the existence of NH_3 and CH_4 molecules into electrical signal and it may be potentially used as an ideal sensor for detection of NH_3 and CH_4 in ambient situation. - Highlights: • Pt-decorated graphene was investigated as an adsorbent for NH_3 and CH_4. • Much higher adsorption of NH_3 and CH_4 on Pt-decorated graphene than pristine graphene. • Higher adsorption of NH_3 compared to CH_4 on Pt-decorated graphene. • Pt influences the electronic structure of graphene.

CO2 Reforming of CH4 by Atmospheric Pressure Abnormal Glow Plasma

International Nuclear Information System (INIS)

Chen Qi; Dai Wei; Tao Xumei; Yu Hui; Dai Xiaoyan; Yin Yongxiang

2006-01-01

A novel plasma atmospheric pressure abnormal glow discharge was used to investigate synthesis gas production from reforming methane and carbon dioxide. Special attentions were paid to the discharge characteristics and CH 4 , CO 2 conversion, H 2 , CO selectivity, and ratio of H 2 /CO varied with the changing of discharging power, the total flux, and the ratio of CH 4 /CO 2 . Experiments were performed in wider operation variables, the discharging power of 240 to 600 W, the CH 4 /CO 2 of 0.2 to 1.0 and the total flux of 140 to 500 mL/min. The experiments showed that the conversion of CH 4 and CO 2 was up to 91.9% and 83.2%, the selectivity of CO and H 2 was also up to 80% and 90% and H 2 /CO mole ratio was 0.2 to 1.2, respectively. A brief analysis for discharge characteristics and the experimental results were given

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

Science.gov (United States)

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

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Quantifying 12/13CH4 migration and fate following sub-surface release to an agricultural soil

International Nuclear Information System (INIS)

Shaw, G.; Atkinson, B.; Meredith, W.; Snape, C.; Steven, M.; Hoch, A.; Lever, D.

2014-01-01

Following gas generation in a Geological Disposal Facility (GDF), 14 C-containing gases could migrate through the geosphere, eventually diffusing into soils at the Earth's surface. This paper reports summary results from laboratory and field experiments to obtain information on the probable rates of a) diffusive transport and b) oxidation of 12/13 CH 4 (as a surrogate for 14 CH 4) in a typical agricultural soil in the UK. Rates of CH 4 oxidation were generally low in the field and undisturbed soil columns, though a re-packed column of homogenised topsoil oxidised ambient atmospheric CH 4 20× faster than an undisturbed soil column. In contrast to low observed rates of CH 4 oxidation, the effective diffusion of CH 4 through the soil was rapid. Isotopically labelled CH 4 injected at a depth of 45 cm in the field diffused to the surface and exited the soil over a time period ranging from 8 to 24 h. The rate of CH 4 diffusion through the soil was increased by the presence of ryegrass roots which increased soil porosity and decreased water content. δ 13 C values for laboratory column soils after labelled CH 4 injection experiments showed no sign of residual 13 C, despite the extremely high δ 13 C values of the injected 12/13 CH 4 . If laboratory observations are confirmed by measurements in field samples it can be concluded that the majority of 14 CH 4 from a GDF which enters a soil with low methanotrophic activity will be lost to the free atmosphere after diffusing rapidly through the soil column

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

Science.gov (United States)

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.

ON THE ORIGIN OF C_4H AND CH_3OH IN PROTOSTELLAR ENVELOPES

International Nuclear Information System (INIS)

Lindberg, Johan E.; Charnley, Steven B.; Cordiner, Martin A.

2016-01-01

The formation pathways of different types of organic molecules in protostellar envelopes and other regions of star formation are subjects of intense current interest. We present here observations of C_4H and CH_3OH, tracing two distinct groups of interstellar organic molecules, toward 16 protostars in the Ophiuchus and Corona Australis molecular clouds. Together with observations in the literature, we present C_4H and CH_3OH data from single-dish observations of 40 embedded protostars. We find no correlation between the C_4H and CH_3OH column densities in this large sample. Based on this lack of correlation, a difference in line profiles between C_4H and CH_3OH, and previous interferometric observations of similar sources, we propose that the emission from these two molecules is spatially separated, with the CH_3OH tracing gas that has been transiently heated to high (∼70–100 K) temperatures and the C_4H tracing the cooler large-scale envelope where CH_4 molecules have been liberated from ices. These results provide insight in the differentiation between hot corino and warm carbon-chain chemistry in embedded protostars.

High rate monitoring CH4 production dynamics and their link with behavioral phases in cattle

OpenAIRE

Blaise, Yannick; Lebeau, Frédéric; Andriamandroso, Andriamasinoro; Beckers, Yves; Heinesch, Bernard; Bindelle, Jérôme

2016-01-01

Microbial fermentation in the rumen produces methane (CH4) which is a loss of energy for ruminants and also contributes to global warming. While the respiration chamber is the standard reference for CH4 emissions quantification, daily CH4 production dynamics can be measured only by steps of 30 min and measurements on pasture are impossible. The alternative method using SF6 as tracer gas can be applied for grazing animals but provides average CH4 production values over at least several hours, ...

Kinetics of the CH3 + HCl/DCl → CH4/CH3D + Cl and CD3 + HCl/DCl → CD3H/CD4 + Cl reactions: An experimental H atom tunneling investigation

International Nuclear Information System (INIS)

Eskola, Arkke J.; Seetula, Jorma A.; Timonen, Raimo S.

2006-01-01

The kinetics of the radical reactions of CH 3 with HCl or DCl and CD 3 with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH 3 (or CD 3 ) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH 3 COCH 3 (or CD 3 COCD 3 ). The decay of CH 3 /CD 3 was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH 3 and CD 3 reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (-E a /RT) (error limits stated are 1σ + Students t values, units in cm 3 molecule -1 s -1 ): k(CH 3 + HCl) = [1.004 + 85.64 exp (-0.02438 x T/K)] x (3.3 ± 1.3) x 10 -13 exp [-(4.8 ± 0.6) kJ mol -1 /RT] and k(CD 3 + HCl) = [1.002 + 73.31 exp (-0.02505 x T/K)] x (2.7 ± 1.2) x 10 -13 exp [-(3.5 ± 0.5) kJ mol -1 /RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (-E a /RT) (error limits stated are 1σ + Students t values, units in cm 3 molecule -1 s -1 ): k(CH 3 + DCl) = (2.4 ± 1.6) x 10 -13 exp [-(7.8 ± 1.4) kJ mol -1 /RT] and k(CD 3 + DCl) = (1.2 ± 0.4) x 10 -13 exp [-(5.2 ± 0.2) kJ mol -1 /RT] cm 3 molecule -1 s -1 . Curvature in the Arrhenius plots of the H-atom abstraction reactions at low temperatures was analyzed by considering H-atom tunneling through the reaction barrier and primary kinetic isotope effect. Contribution of tunneling in it was concluded to be negligible. In addition, secondary isotope effect was measured

Method for indirect quantification of CH4 production via H2O production using hydrogenotrophic methanogens

Directory of Open Access Journals (Sweden)

Ruth-Sophie eTaubner

2016-04-01

Full Text Available ydrogenotrophic methanogens are an intriguing group of microorganisms from the domain Archaea. They exhibit extraordinary ecological, biochemical, physiological characteristics colorbox{yellow}{and have a huge biotechnological potential}. Yet, the only possibility to assess the methane (CH$_4$ production potential of hydrogenotrophic methanogens is to apply gas chromatographic quantification of CH$_4$.In order to be able to effectively screen pure cultures of hydrogenotrophic methanogens regarding their CH$_4$ production potential we developed a novel method for indirect quantification of colorbox{yellow}{the} volumetric CH$_4$ production rate by measuring colorbox{yellow}{the} volumetric water production rate. This colorbox{yellow}{ } method was established in serum bottles for cultivation of methanogens in closed batch cultivation mode. Water production was colorbox{yellow}{estimated} by determining the difference in mass increase in an isobaric setting.This novel CH$_4$ quantification method is an accurate and precise analytical technique, colorbox{yellow}{which can be used} to rapidly screen pure cultures of methanogens regarding colorbox{yellow}{their} volumetric CH$_{4}$ evolution rate. colorbox{yellow}{It} is a cost effective alternative colorbox{yellow}{determining} CH$_4$ production of methanogens over CH$_4$ quantification by using gas chromatography, especially if colorbox{yellow}{ } applied as a high throughput quantification method. colorbox{yellow}{Eventually, the} method can be universally applied for quantification of CH$_4$ production from psychrophilic, thermophilic and hyperthermophilic hydrogenotrophic methanogens.

Rotational study of the CH4–CO complex: Millimeter-wave measurements and ab initio calculations

International Nuclear Information System (INIS)

Surin, L. A.; Tarabukin, I. V.; Panfilov, V. A.; Schlemmer, S.; Kalugina, Y. N.; Faure, A.; Rist, C.; Avoird, A. van der

2015-01-01

The rotational spectrum of the van der Waals complex CH 4 –CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110–145 GHz. Newly observed and assigned transitions belong to the K = 2–1 subband correlating with the rotationless j CH4 = 0 ground state and the K = 2–1 and K = 0–1 subbands correlating with the j CH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH 4 –CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH 4 –CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH 4 face closest to the CO subunit and binding energy D e = 177.82 cm −1 . The bound rovibrational levels of the CH 4 –CO complex were calculated for total angular momentum J = 0–6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D 0 are 91.32, 94.46, and 104.21 cm −1 for A (j CH4 = 0), F (j CH4 = 1), and E (j CH4 = 2) nuclear spin modifications of CH 4 –CO, respectively

Facile And Reversible Co Insertion Into The Ir-ch3 Bond Of [ir4(ch3)(co)8(μ4- η3-ph2pccph)(μ-pph2)

OpenAIRE

Vargas M.D.; Pereira R.M.S.; Braga D.; Grepioni F.

1993-01-01

Reaction of [Ir4H(CO)10(mu-PPh2)) with BuLi, Ph2PC=CPh and then Mel gives [Ir4(CH3)(CO)8(mu4-eta3-Ph2PCCPh)(mu-PPh2)], which undergoes a reversible two-step CO insertion under extremely mild conditions to yield Ir4{(CH3C(O)}(CO)8-(mu4:eta3-Ph2PCCPh)(mu-PPh2)] as the final product; the structures of both species have been established by X-ray diffraction studies.

Automatic installation of separating 13CH4 from natural CH4, representing a profiled cascade, achieved on the basis of the thermodiffusion column study

International Nuclear Information System (INIS)

Ghete, P.

1976-01-01

In order to enrich 13 CH 4 from natural CH 4 , an installation, partly automated, has been achieved, using thermodifussion as a separation process for stable isotopes. The thermodifussion columns is original both as construction and solution used for heating the concentric tube. It has been studied the heat transfer properties of the column, the mass transfer and it has been realized an original calculation program concerning the T.D. cascade performances, pointing out an energetical optimum. The experimental results are presented in diagrams each point representing the result of the statistical processing of at least 10 experimental measurements. (author)

Experimental confirmation of the Jahn-Teller distortion of CH4+

International Nuclear Information System (INIS)

Gemmell, D.S.; Kanter, E.P.; Pietsch, W.J.

1979-01-01

Measured energy and angular distributions are reported for H + and C/sup n+/ (n = 2,3,4) fragments resulting from the collisional dissociation of 200-keV/amu CH/sub m/ + (m = 0 to 4) in thin carbon targets. From the systematic trends of these Coulomb explosion spectra, qualitative information can be obtained on the structures of these species. In particular, the series displays a narrowing of the carbon angular and energy widths as protons are symmetrically added around a central carbon atom and provide a focusing effect. Because of the Jahn-Teller distortion, the carbon width in CH 4 + is dramatically increased. 8 references

Synthesis and thermolysis of Cp*(C5Me4CH2)TiR complexes

NARCIS (Netherlands)

Luinstra, GA; Brinkmann, PHP; Teuben, JH; Luinstra, Gerrit A.

1997-01-01

Substitution of the chloride in Cp*FvTiCl with MR (Fv = C5Me4CH2; R = Me, CH2SiMe3, CH2CMe3, CH = CH2, M = Li; R = CH2Ph, M = K; R = C3H5, M = MgCl; R = Ph, M = Na . NaCl) gives Cp*FvTiR. NMR spectroscopic evidence points towards a series of structurally related compounds with a bent-sandwich

Large CO2 and CH4 release from a flooded formerly drained fen

Science.gov (United States)

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.

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

OpenAIRE

Spokas, Kurt; Bogner, Jean; Corcoran, Meg; Walker, Scott

2015-01-01

Abstract Improved quantification of diverse CH4 sources at the urban scale is needed to guide local 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 landfill CH4 generation (methanogenesis), but does not explicitly consider climate or soil dependencies for emissions. Relying on a comprehensive California landfill database, a field-validated process-based m...

4-(2-Tetrathiafulvalenyl-ethenyl)pyridine (TTF-CH=CH-Py) radical cation salts containing poly(beta-diketonate) rare earth complexes: synthesis, crystal structure, photoluminescent and magnetic properties.

Science.gov (United States)

Pointillart, Fabrice; Maury, Olivier; Le Gal, Yann; Golhen, Stéphane; Cador, Olivier; Ouahab, Lahcène

2009-08-03

The reactions between the redox-active 4-(2-tetrathiafulvalenyl-ethenyl)pyridine ligand (TTF-CH=CH-Py) and the tris(1,1,1,5,5,5-hexafluoroacetylacetonate)Ln(III) (Ln = La and Nd) lead to the formation of compounds with the formulas {[La(hfac)(5)][(TTF-CH=CH-Py(*+))](2)} (1), {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2) (2), and {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2)(H(2)O)(C(6)H(14))(0.5) (3) (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion). These compounds have been characterized by single-crystal X-ray diffraction, optical, and magnetic measurements. Compounds 1, 2, and 3 crystallize in the monoclinic C2/c, triclinic P1, and monoclinic P2(1)/c space groups, respectively. La(III) adopts a tetradecahedral geometry, while Nd(III) stands in a distorted capped square antiprism one. In 1, the inorganic network is formed by the [La(hfac)(5)](2-) dianionic complexes, while it is formed by a pseudo-dimeric dianionic unit of formula {[Nd(hfac)(4)(H(2)O)](2)}(2-) in 2 and 3. In all crystal structures, the organic network is constituted by the TTF-CH=CH-Py(*+) radical cations. The inorganic and organic networks interact through intermolecular contacts between the pyridine moieties of the TTF-CH=CH-Py(*+) radical cations and the Ln(III) ions. The luminescence properties of the Nd(III) ions (9400 cm(-1)) and fluorescence band of the TTF-CH=CH-Py(*+) radical cations (10200 cm(-1)) have been observed and studied for compound 2. Complexes 2 and 3 are paramagnetic because of Nd(III) ions. Compound 2 is a paramagnetic luminescent TTF-radical-cation-based material. Resistivity measurements have also been performed on these materials.

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

Science.gov (United States)

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

Science.gov (United States)

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

Science.gov (United States)

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.

Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

Science.gov (United States)

Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

2014-09-18

We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

How to oxidize atmospheric CH4? - A challenge for the future

International Nuclear Information System (INIS)

Chazelas, Bruno; Leger, Alain; Ollivier, Marc

2006-01-01

Methane is an active Greenhouse effect gas whose concentration will likely increase in the future. The possible destabilisation of CH 4 clathrates (hydrates) due to anthropogenic climate warming, and the resulting outgasing of methane, could lead to a major increase of the global Greenhouse effect, with dramatic consequences for Humanity. For these reasons, the study of possible countermeasures should be actively considered. Here, we suggest taking advantage of the thermodynamic instability of CH 4 in air, and search for ways to oxidize it

Biotic controls on CO2 and CH4 exchange in wetlands - a closed environment study

DEFF Research Database (Denmark)

Christensen, TR; Panikov, N; Mastepanov, M

2003-01-01

Wetlands are significant sources of the important greenhouse gas CH4. Here we explore the use of an experimental system developed for the determination of continuous fluxes of CO2 and CH4 in closed ecosystem monoliths including the capture of (CO2)-C-14 and (CH4)-C-14 following pulse labelling...... with (CO2)-C-14. We show that, in the ecosystem studied, ebullition (bubble emission) may account for 18 to 50% of the total CH4 emission, representing fluxes that have been difficult to estimate accurately in the past. Furthermore, using plant removal and C-14 labelling techniques, we use the system....../atmosphere interactions, including possible feedback effects on climate change. In recent years much attention has been devoted to ascertaining and subsequently using the relationship between net ecosystem productivity and CH4 emission as a basis for extrapolation of fluxes across large areas. The experimental system...

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

Science.gov (United States)

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

Annual variation of CH{sub 4} emissions from the middle taiga in West Siberian Lowland (2005-2009): a case of high CH{sub 4} flux and precipitation rate in the summer of 2007

Energy Technology Data Exchange (ETDEWEB)

Sasakawa, M.; Ito, A.; Machida, T. (Center for Global Environmental Research, National Inst. for Environmental Studies, Tsukuba (Japan)), Email: sasakawa.motoki@nies.go.jp; Tsuda, N. (Global Environmental Forum, Bunkyo-ku Tokyo (Japan)); Niwa, Y. (Meteorological Research Inst., Tsukuba (Japan)); Davydov, D.; Fofonov, A.; Arshinov, M. (V.E. Zuev Inst. of Atmospheric Optics, Russian Academy of Sciences, Siberian Branch, Tomsk (Russian Federation))

2012-03-15

We described continuous measurements of CH{sub 4} and CO{sub 2} concentration obtained at two sites placed in the middle taiga, Karasevoe (KRS) and Demyanskoe (DEM), in West Siberian Lowland (WSL) from 2005 to 2009. Although both CH{sub 4} and CO{sub 2} accumulation (DELTACH{sub 4} and DELTACO{sub 2}) during night-time at KRS in June and July 2007 showed an anomalously high concentration, higher ratios of DELTACH{sub 4}/DELTACO{sub 2} compared with those in other years indicated that a considerably higher CH{sub 4} flux occurred relative to the CO{sub 2} flux. The daily CH{sub 4} flux calculated with the ratio of DELTACH{sub 4}/DELTACO{sub 2} and terrestrial biosphere CO{sub 2} flux from an ecosystem model showed a maximum in July at the both sites. Although anomalously high flux was observed in June and July 2007 at KRS, only a small flux variation was observed at DEM. The high regional CH{sub 4} flux in June and July 2007 at KRS was reproduced using a process-based ecosystem model, Vegetation Integrative Simulator for Trace gases (VISIT), in response to high water table depth caused by the anomalously high precipitation during the summer of 2007

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

International Nuclear Information System (INIS)

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

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 (CH 4 ), a potent greenhouse gas. To examine the effects of lowland permafrost thaw over millennial timescales, we measured carbon dioxide (CO 2 ) and CH 4 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 CH 4 exchange in July (123 ± 71 mg CH 4 –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 CH 4 –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 CH 4 –C m −2 d −1 in July). Carbon lost via CH 4 efflux during the growing season at these intermediate age sites was 8% of uptake by net ecosystem exchange. Our results provide evidence that CH 4 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 CH 4 emission, CO 2 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 CH 4 emission to the atmosphere that must be considered for a complete understanding of high latitude CH 4 dynamics. (paper)

CO2 and CH4 exchange by Phragmites australis under different climates

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

H. Jamali

2013-04-01

Full Text Available 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

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

Science.gov (United States)

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

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

Science.gov (United States)

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.

Optimisation of expansion liquefaction processes using mixed refrigerant N_2–CH_4

International Nuclear Information System (INIS)

Ding, He; Sun, Heng; He, Ming

2016-01-01

Highlights: • A refrigerant composition matching method for N_2–CH_4 expansion processes. • Efficiency improvements for propane pre-cooled N_2–CH_4 expansion processes. • The process shows good adaptability to varying natural gas compositions. - Abstract: An expansion process with a pre-cooling system is simulated and optimised by Aspen HYSYS and MATLAB"™. Taking advantage of higher specific refrigeration effect of methane and easily reduced refrigeration temperature of nitrogen, the designed process adopts N_2–CH_4 as a mixed refrigerant. Based on the different thermodynamic properties and sensitivity difference of N_2 and CH_4 over the same heat transfer temperature range, this work proposes a novel method of matching refrigerant composition which aims at single-stage or multi-stage series expansion liquefaction processes with pre-cooling systems. This novel method is applied successfully in propane pre-cooled N_2–CH_4 expansion process, and the unit power consumption is reduced to 7.09 kWh/kmol, which is only 5.35% higher than the global optimised solutions obtained by genetic algorithm. This novel method can fulfil the accomplishments of low energy consumption and high liquefaction rate, and thus decreases the gap between the mixed refrigerant and expansion processes in energy consumption. Furthermore, the high exergy efficiency of the process indicates good adaptability to varying natural gas compositions.

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

Science.gov (United States)

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 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.

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

Science.gov (United States)

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 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.

Phase transitions in solid Kr-CH4 solutions and rotational excitations in phase II

International Nuclear Information System (INIS)

Bagatskii, M.I.; Mashchenko, D.A.; Dudkin, V.V.

2007-01-01

The heat capacity C p of solid Kr-n CH 4 solutions with the CH 4 concentrations n=0.82, 0.86, 0.90 as well as solutions with n=0.90, 0.95 doped with 0.002 O 2 impurity has been investigated under equilibrium vapor pressure over the internal 1-24 K. The (T,n)-phase diagram was refined and the region of two-phase states was determined for Kr-n CH 4 solid solutions. The contribution of the rotational subsystem, C r ot, to the heat capacity of the solutions has been separated. Analysis of C r ot(T) at T 1 and E 2 between the tunnel levels of the A-, T- and A-, E--nuclear-spin species of CH 4 molecules in the orientationally ordered subsystem, and to determine the effective energy gaps E 1 between lowest levels of the A- and T- species. The relations τ(n) and E 1 (n) stem from changes of the effective potential field caused as the replacement of CH 4 molecules by Kr atoms at sites of the ordered sublattices. The effective gaps E L between a group of tunnel levels of the ground-state liberation state and the nearest group of excited levels of the liberation state of the ordered CH 4 molecules in the solutions with n=0.90 (E L =52 K) and 0.95 (E L =55 K) has been estimated

In-situ studies of microbial CH4 oxidation efficiency in Arctic wetland soils. Applications of stable carbon isotopes

International Nuclear Information System (INIS)

Preuss, Inken-Marie

2013-01-01

Arctic wetland soils are significant sources of the climate-relevant trace gas methane (CH 4 ). The observed accelerated warming of the Arctic is expected to cause deeper permafrost thawing followed by increased carbon mineralization and CH 4 formation in water-saturated permafrost-affected tundra soils thus creating a positive feedback to climate change. Aerobic CH 4 oxidation is regarded as the key process reducing CH 4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. This study improved the in-situ quantification of microbial CH 4 oxidation efficiency in arctic wetland soils in Russia's Lena River Delta based on stable isotope signatures of CH 4 . In addition to the common practice of determining the stable isotope fractionation during oxidation, additionally the fractionation effect of diffusion, an important gas transport mechanism in tundra soils, was investigated for both saturated and unsaturated conditions. The isotopic fractionation factors α ox and α diff were used to calculate the CH 4 oxidation efficiency from the CH 4 stable isotope signatures of wet polygonal tundra soils of different hydrology. Further, the method was used to study the short-term effects of temperature increase with a climate manipulation experiment. For the first time, the stable isotope fractionation of CH 4 diffusion through water-saturated soils was determined with α diff = 1.001 ± 0.0002 (n = 3). CH 4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was α diff = 1.013 ± 0.003 (n = 18). For the studied sites the fractionation factor for diffusion under saturated conditions α diff = 1.001 seems to be of utmost importance for the quantification of the CH 4 oxidation efficiency, since most of the CH 4 is oxidized in the saturated part at the aerobic-anaerobic interface. Furthermore, it was found that α ox differs widely between sites and horizons (mean α ox = 1

Correlations among atmospheric CO[sub 2], CH[sub 4] and CO in the Arctic, March 1989

Energy Technology Data Exchange (ETDEWEB)

Conway, T.J.; Steele, L.P.; Novelli, P.C. (NOAA Climate Monitoring and Diagnostics Lab., Boulder, CO (United States))

1993-12-01

During six aircraft flights conducted as part of the third Arctic Gas and Aerosol Sampling Program (AGASP III, March 1989), 189 air samples were collected throughout the Arctic troposphere and lower stratosphere for analysis of CO[sub 2], CH[sub 4] and CO. The mixing ratios of the three gases varied significantly both horizontally and vertically. Elevated concentrations were found in layers with high anthropogenic aerosol concentrations (Arctic Haze). The mixing ratios of CO[sub 2], CH[sub 4] and CO were highly correlated on all flights. A linear regression of CH[sub 4] vs CO[sub 2] for pooled data from all flights yielded a correlation coefficient (r[sup 2]) of 0.88 and a slope of 13.5 ppb CH[sub 4]/ppm CO[sub 2] (n 186). For CO vs CO[sub 2] a pooled linear regression gave r[sup 2] 0.91 and a slope of 15.8 ppb CO/ppm CO[sub 2] (n 182). Carbon dioxide CH[sub 4] and CO also exhibited mean vertical gradients with slopes of 0.37, -4.4 and -4.2 ppb km[sup -1], respectively. Since the carbon dioxide variations observed in the Arctic atmosphere during winter are due primarily to variations in the emissions and transport of anthropogenic CO[sub 2] from Europe and Asia, the strong correlations that we have found suggest that a similar interpretation applies to CH[sub 4] and CO. Using reliable estimates of CO[sub 2] emissions for the source regions and the measured CH[sub 4]/CO[sub 2] and CO/CO[sub 2] ratios, we estimate a regional European CH[sub 4] source of 47[+-] 6 Tg CH[sub 4] yr[sup -1] that may be associated with fossil fuel combustion. A similar calculation for CO results in an estimated regional CO source of 82[+-]2 Tg CO yr[sup -1]. 31 refs., 7 figs., 4 tabs.

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

Science.gov (United States)

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

Science.gov (United States)

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

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

Directory of Open Access Journals (Sweden)

J. van Huissteden

2011-10-01

Full Text Available 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

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

Science.gov (United States)

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

Formation of H2 and CH4 by weathering of olivine at temperatures between 30 and 70°C

Directory of Open Access Journals (Sweden)

Crill Patrick

2011-06-01

Full Text Available Abstract Hydrocarbons such as CH4 are known to be formed through the Fischer-Tropsch or Sabatier type reactions in hydrothermal systems usually at temperatures above 100°C. Weathering of olivine is sometimes suggested to account for abiotic formation of CH4 through its redox lowering and water splitting properties. Knowledge about the CH4 and H2 formation processes at low temperatures is important for the research about the origin and cause of early Earth and Martian CH4 and for CO2 sequestration. We have conducted a series of low temperature, long-term weathering experiments in which we have tested the CH4 and H2 formation potential of forsteritic olivine. The results show low temperature CH4 production that is probably influenced by chromite and magnetite as catalysts. Extensive analyses of a potential CH4 source trapped in the crystal structure of the olivine showed no signs of incorporated CH4. Also, the available sources of organic carbon were not enough to support the total amount of CH4 detected in our experiments. There was also a linear relationship between silica release into solution and the net CH4 accumulation into the incubation bottle headspaces suggesting that CH4 formation under these conditions could be a qualitative indicator of olivine dissolution. It is likely that minerals such as magnetite, chromite and other metal-rich minerals found on the olivine surface catalyze the formation of CH4, because of the low temperature of the system. This may expand the range of environments plausible for abiotic CH4 formation both on Earth and on other terrestrial bodies.

Betaine Phosphate (CH3)3N+CH2COO-.H3PO4 Modification Using D2O

International Nuclear Information System (INIS)

Saryati; Ridwan; Deswita; Sugiantoro, Sugik

2002-01-01

Betaine fosfate (CH 3 ) 3 N + CH 2 COO - .H 3 PO 4 modification by using D 2 O has been studied. This modification was carried out by slowly evaporation the saturated Betaine phosphat in the D 2 O solution in the dry box at 40 o C, until the dry crystal were formed. Based on the NMR data, can be concluded that the exchange process with D has been runed well and Betaine phosphate-D (CH 3 ) 3 N + CH 2 COO - .H 3 PO 4 has been resulted. From the X-ray diffraction pattern data can be concluded that there are a deference in the crystal structure between Betaine phosphate and Betaine phosphate modification result. From the Differential Scanning Colorimeter (DSC) diagram at the range temperature from 30 o C to 250 o C, can be shown that the Betaine phosphate-H has two endothermic transition phase, at 99 o C with a very little adsorbed calor and at 221.50 o C with -26.75 cal/g. Modified Betaine phosphate has also two endothermic transition phase, at 99.86 o C with -1.94 cal/g and at 171.01 o C with -3.48 cal/g. It can be conclosed that the D atom substitution on the H atoms in Betaine phosphate, to change the crystal and the endothermic fase temperature and energy

Transport Mechanisms for CO2-CH4 Exchange and Safe CO2 Storage in Hydrate-Bearing Sandstone

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Knut Arne Birkedal

2015-05-01

Full Text Available CO2 injection in hydrate-bearing sediments induces methane (CH4 production while benefitting from CO2 storage, as demonstrated in both core and field scale studies. CH4 hydrates have been formed repeatedly in partially water saturated Bentheim sandstones. Magnetic Resonance Imaging (MRI and CH4 consumption from pump logs have been used to verify final CH4 hydrate saturation. Gas Chromatography (GC in combination with a Mass Flow Meter was used to quantify CH4 recovery during CO2 injection. The overall aim has been to study the impact of CO2 in fractured and non-fractured samples to determine the performance of CO2-induced CH4 hydrate production. Previous efforts focused on diffusion-driven exchange from a fracture volume. This approach was limited by gas dilution, where free and produced CH4 reduced the CO2 concentration and subsequent driving force for both diffusion and exchange. This limitation was targeted by performing experiments where CO2 was injected continuously into the spacer volume to maintain a high driving force. To evaluate the effect of diffusion length multi-fractured core samples were used, which demonstrated that length was not the dominating effect on core scale. An additional set of experiments is presented on non-fractured samples, where diffusion-limited transportation was assisted by continuous CO2 injection and CH4 displacement. Loss of permeability was addressed through binary gas (N2/CO2 injection, which regained injectivity and sustained CO2-CH4 exchange.

Regional scale variations of atmospheric CO2 and CH4 from satellite observation

International Nuclear Information System (INIS)

Ru, F; Lei, L; Guan, X; Bu, R; Qi, J

2014-01-01

To identify the sources, sinks and changes of atmospheric CO 2 and CH 4 , this study investigates the spatio-temporal changes of atmospheric CO 2 and CH 4 concentration on the regional scale by the satellite observations. In this paper, choosing the land region of China as the study area, we investigate the spatio-temporal changes of atmospheric CO 2 and CH 4 concentrations using the data of the CO 2 dry air mixing ratio (XCO 2 ), and the CH 4 dry air mixing ratio (XCH 4 ), retrieved by the Greenhouse Gases Observing Satellite (GOSAT) from Jan. 2010 to Dec. 2012. The results show that (1) both XCO 2 and XCH 4 show higher concentrations in southeastern regions than that in the northwestern, and tend to yearly increasing from 2010 to 2013; (2) XCO 2 shows obvious seasonal change with higher values in the spring than that in summer. The seasonal peak-to-peak amplitude is 8 ppm and the annual growth is about 2 ppm. XCH 4 , however, does not show a seasonal change; (3) With regard to different land-use backgrounds, XCO 2 shows larger concentrations over the areas of urban agglomeration than that over the grasslands and deserts, and XCH 4 shows lower concentrations over deserts than that over the Yangtze River Delta region and Sichuan Basin

Ion imaging study of reaction dynamics in the N{sup +}+ CH{sub 4} system

Energy Technology Data Exchange (ETDEWEB)

Pei, Linsen; Farrar, James M. [Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)

2012-10-21

The velocity map ion imaging method is applied to the ion-molecule reactions of N{sup +} with CH{sub 4}. The velocity space images are collected at collision energies of 0.5 and 1.8 eV, providing both product kinetic energy and angular distributions for the reaction products CH{sub 4}{sup +}, CH{sub 3}{sup +}, and HCNH{sup +}. The charge transfer process is energy resonant and occurs by long-range electron transfer that results in minimal deflection of the products. The formation of the most abundant product, CH{sub 3}{sup +}, proceeds by dissociative charge transfer rather than hydride transfer, as reported in earlier publications. The formation of HCNH{sup +} by C-N bond formation appears to proceed by two different routes. The triplet state intermediates CH{sub 3}NH{sup +} and CH{sub 2}NH{sub 2}{sup +} that are formed as N{sup +}({sup 3}P) approaches CH{sub 4} may undergo sequential loss of two hydrogen atoms to form ground state HCNH{sup +} products on a spin-allowed pathway. However, the kinetic energy distributions for formation of HCNH{sup +} extend past the thermochemical limit to form HCNH{sup +}+ 2H, implying that HCNH{sup +} may also be formed in concert with molecular hydrogen, and requiring that intersystem crossing to the singlet manifold must occur in a significant ({approx}25%) fraction of reactive collisions. We also report GAUSSIAN G2 calculations of the energies and structures of important singlet and triplet [CNH{sub 4}{sup +}] complexes that serve as precursors to product formation.

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

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

Lee, Mal-Soon [Physical; McGrail, B. Peter [Physical; Rousseau, Roger [Physical; Glezakou, Vassiliki-Alexandra [Physical

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 less 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.

Accurate quantum calculations of the reaction rates for H/D+ CH4

NARCIS (Netherlands)

Harrevelt, R. van; Nyman, G.; Manthe, U.

2007-01-01

In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H+CH4 -> CH3+H-2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with

Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

DEFF Research Database (Denmark)

Hurley, MD; Ball, JC; Wallington, TJ

2004-01-01

Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH...... respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration......, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27...

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

Science.gov (United States)

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 (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.

CO2 and CH4 in sea ice from a subarctic fjord under influence of riverine input

DEFF Research Database (Denmark)

Crabeck, O.; Delille, B.; Thomas, D. N.

2014-01-01

We present CH4 concentration [CH4] and the partial pressure of CO2 (pCO2) in bulk sea ice from subarctic, land-fast sea ice in the Kapisillit fjord, Greenland. The bulk ice [CH4] ranged from 1.8 to 12.1 nmol L−1, which corresponds to a partial pressure range of 3 to 28 ppmv. This is markedly higher......-saturated compared to the atmosphere (390 ppmv). Our study adds to the few existing studies of CH4 and CO2 in sea ice and concludes that sub-arctic sea can be a sink for atmospheric CO2, while being a net source of CH4. Processes related to the freezing and melting of sea ice represents large unknowns...... to the exchange of CO2 but also CH4. It is therefore imperative to assess the consequences of these unknowns through further field campaigns and targeted research under other sea ice conditions at both hemispheres....

Surface study of platinum decorated graphene towards adsorption of NH{sub 3} and CH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Rad, Ali Shokuhi, E-mail: a.shokuhi@gmail.com [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Pazoki, Hossein; Mohseni, Soheil [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Zareyee, Daryoush [Department of Chemistry, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Peyravi, Majid [Faculty of Chemical Engineering, Babol University of Technology, Babol (Iran, Islamic Republic of)

2016-10-01

To distinguish the potential of graphene sensors, there is a need to recognize the interaction between graphene sheet and adsorbing molecules. We used density functional theory (DFT) calculations to study the properties of pristine as well as Pt-decorated graphene sheet upon adsorption of NH{sub 3} and CH{sub 4} on its surface to exploit its potential to be as gas sensors for them. We found much higher adsorption, higher charge transfer, lower intermolecular distance, and higher orbital hybridizing upon adsorption of NH{sub 3} and CH{sub 4} gas molecules on Pt-decorated graphene compared to pristine graphene. Also our calculations reveal that the adsorption energies on Pt-decorated graphene sheet are in order of NH{sub 3} >CH{sub 4} which could be corresponded to the order of their sensitivity on this modified surface. We used orbital analysis including density of states as well as frontier molecular orbital study for all analyte-surface systems to more understanding the kind of interaction (physisorption or chemisorption). Consequently, the Pt-decorated graphene can transform the existence of NH{sub 3} and CH{sub 4} molecules into electrical signal and it may be potentially used as an ideal sensor for detection of NH{sub 3} and CH{sub 4} in ambient situation. - Highlights: • Pt-decorated graphene was investigated as an adsorbent for NH{sub 3} and CH{sub 4}. • Much higher adsorption of NH{sub 3} and CH{sub 4} on Pt-decorated graphene than pristine graphene. • Higher adsorption of NH{sub 3} compared to CH{sub 4} on Pt-decorated graphene. • Pt influences the electronic structure of graphene.

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

Science.gov (United States)

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...

Factors affecting variation in CH4 emission from paddy soils grown with different rice cultivars: A pot experiment

Science.gov (United States)

Watanabe, Akira; Kimura, Makoto

1998-08-01

The growth of rice plants greatly influences CH4 emission from paddy fields through the supply of organic materials such as root exudates and sloughed tissues, the release of oxygen to the root environment, and the transfer of CH4 from the rhizosphere into the atmosphere through the aerenchyma. In the present pot experiments, the effects of the release of water-soluble organic substances from roots, the air space in roots, and the CH4-oxidizing capacity of roots on intervarietal differences in CH4 emission were examined using three Japonica type cultivars (Norin 25, Nipponbare, and Aoinokaze), which differ in morphological properties. The CH4 emission rates varied among the cultivars from mid-July (tillering stage) to the beginning of September (heading stage).Total CH4 emission throughout the rice growth period was largest for Norin 25, followed by Nipponbare, and Aoinokaze. In August, the rate of release of water-soluble organic substances from roots was largest for Norin 25. The air space in roots was also largest in Norin 25 and least in Aoinokaze. The stable carbon isotopic ratios (δ13C) of CH4 in roots were 3-10‰ higher than those in soil in August. The difference in δ13C values of CH4 between roots and soil was largest for Aoinokaze and smallest for Norin 25. In September, the difference in δ13C values of CH4 between roots and soil became small (2-3‰). These findings suggest that the proportion of CH4 oxidation in the rhizosphere was largest in the cultivar which emitted the smallest amount of CH4 and that the proportion became smaller with continued plant growth.

Studies on the adsorption behavior of CO2-CH4 mixtures using activated carbon

Directory of Open Access Journals (Sweden)

R. B. Rios

2013-12-01

Full Text Available Separation of CO2 from CO2-CH4 mixtures is an important issue in natural gas and biogas purification. The design of such separation processes depends on the knowledge of the behavior of multicomponent adsorption, particularly that of CO2-CH4 mixtures. In this study, we present a series of experimental binary equilibrium isotherms for CO2-CH4 mixtures on an activated carbon at 293 K and compare them with predicted values using the Ideal Adsorption Solution Theory (IAST and the Extended Langmuir (EL model. Even at concentrations of ca. 20% for all binary isotherms, CO2 already presents higher adsorbed amounts with respect to CH4. A maximum selectivity of around 8.7 was observed for a nearly equimolar mixture at 0.1 MPa. The IAST in conjunction with the Toth equation showed slightly better results than IAST using the Langmuir equation and both showed better results than the EL model.

Intermolecular Force Field Parameters Optimization for Computer Simulations of CH4 in ZIF-8

Directory of Open Access Journals (Sweden)

Phannika Kanthima

2016-01-01

Full Text Available The differential evolution (DE algorithm is applied for obtaining the optimized intermolecular interaction parameters between CH4 and 2-methylimidazolate ([C4N2H5]− using quantum binding energies of CH4-[C4N2H5]− complexes. The initial parameters and their upper/lower bounds are obtained from the general AMBER force field. The DE optimized and the AMBER parameters are then used in the molecular dynamics (MD simulations of CH4 molecules in the frameworks of ZIF-8. The results show that the DE parameters are better for representing the quantum interaction energies than the AMBER parameters. The dynamical and structural behaviors obtained from MD simulations with both sets of parameters are also of notable differences.

Quantifying Gas Flaring CH4 Consumption Using VIIRS

Directory of Open Access Journals (Sweden)

Xiaodong Zhang

2015-07-01

Full Text Available A method was developed to estimate the consumption of CH4 and the release of CO2 by gas flaring using VIIRS nighttime data. The results agreed with the field data collected at six stations in Bakken field, North Dakota, USA, within ±50%, as measured by mean relative errors and with a correlation coefficient of 0.75. This improved over the NOAA NightFire estimates, likely due to: (1 more stringent data selection using only the middle portion of cloud-free VIIRS nighttime imagery; (2 the use of a lower heating rate, which is more suitable for the field condition; and (3 more accurate efficiency factors in calculating completeness in combustion and conversion of total reaction energy into radiant energy that can be sensed by a satellite sensor. While using atmospherically-corrected data can further improve the estimate of CH4 consumption by ~10%, the major uncertainty remains as being the form factor of the flares, particularly the ratio of total surface area of a flare to the cross-section area that was seen by a satellite sensor.

EMISSION ASSESSMENT AT THE ŠTĚPÁNOVICE MUNICIPAL SOLID WASTE LANDFILL FOCUSING ON CH4 EMISSIONS

Directory of Open Access Journals (Sweden)

Dana Adamcová

2016-07-01

Full Text Available The study was conducted to measure the emission from landfill in the years 2005–2011. The results are used to diagnose the emissions of CH4. The mean value of CH4 in vol. % in the collection wells ranged from 0 to 2.14 vol. % the mean concentration of CH4 in mg/m3 ranged from 0 to 25 251 mg/m3 the average concentration of CH4 in mg/Nm3 at the measuring and control points ranged from 2.2 to 24.1 mg/Nm3. CH4 emissions from the landfill do not exceed the reporting thresholds the landfill does not meet conditions for being included in the Integrated Register of Pollutants.

Sensitizing effects of NOx on CH4 oxidation at high pressure

DEFF Research Database (Denmark)

Rasmussen, Christian Lund; Rasmussen, Anja Egede; Glarborg, Peter

2008-01-01

The CH4/O2/NOx system is investigated in a laboratory-scale high pressure laminar flow reactor with the purpose of elucidating the sensitizing effects of NOx on CH4 oxidation at high pressures and medium temperatures. Experiments are conducted at 100, 50, and 20 bar, 600-900 K, and stoichiometric...... ratios ranging from highly reducing to oxidizing conditions. The experimental results are interpreted in terms of a detailed kinetic model drawn from previous work of the authors, including an updated reaction subset for the direct interactions of NOx and C1-2 hydrocarbon species relevant...

Super Rice Cropping Will Enhance Rice Yield and Reduce CH4 Emission: A Case Study in Nanjing, China

Directory of Open Access Journals (Sweden)

Yu JIANG

2013-11-01

Full Text Available A pot experiment was performed to learn the differences in plant productivity and CH4 emission between two rice cultivars, super rice variety Ningjing 1 and traditional variety Zhendao 11, which were currently commercially applied in Nanjing, China. Similar seasonal changes of CH4 emission fluxes and soil solution CH4 contents were found between the tested cultivars. Although there was no significant difference in plant biomass production between the cultivars, the grain yield of Ningjing 1 was significantly higher by 35.0% (P < 0.05 than that of Zhendao 11, whereas the total CH4 emission from Ningjing 1 was 35.2% lower (P < 0.05. The main difference in the amounts of CH4 emission between the cultivars occurred in the period from the tillering stage to the heading stage. The biomass-scaled and yield-scaled CH4 emissions were respectively 3.8 and 5.2 mg/g for Ningjing 1, significantly lower than those for Zhendao 11 (7.4 and 12.8 mg/g, respectively. According to the relationships between the plant growth characteristics and the CH4 emission, a stronger root system contributed mainly to the lower CH4 emission of Ningjing 1, as compared with Zhendao 11. Our results demonstrated that super rice has advantages not only in grain productivity but also in CH4 emission mitigation. Further expansion of super rice cropping will enhance rice yield and reduce greenhouse gas emission in China.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Influence of atmospheric stability and transport on CH{sub 4} concentrations in northern Spain

Energy Technology Data Exchange (ETDEWEB)

García, M. Ángeles, E-mail: magperez@fa1.uva.es; Sánchez, M. Luisa; Pérez, Isidro A.; Ozores, Marta I.; Pardo, Nuria

2016-04-15

Continuous methane (CH{sub 4}) concentrations were measured in Northern Spain over two years (2011–2012) by multi-point sampling at 1.8, 3.7 and 8.3 m using a Picarro analyser. The technique is based on cavity ring-down spectroscopy. The contrast in mean concentrations was about 1.2 ppb, with 95th percentiles differing by 2.2 ppb and mean minimum concentrations proving similar. Temporal variations of CH{sub 4} were also analysed, with a similar seasonal variability being found for the three heights. The highest CH{sub 4} concentrations were obtained in late autumn and winter and the lowest in summer, yielding a range of 52 ppb. This variation may depend on the active photochemical reaction with OH radical during a period of intense solar radiation and changes in soil conditions together with variations in emissions. Peak concentration levels were recorded at night-time, between 5:00–7:00 GMT, with mean values ranging between 1920 and 1923 ppb. The lowest value, around 1884 ppb, was obtained at 16:00 GMT. This diurnal variation was mainly related to vertical mixing and photochemistry. Therefore, CH{sub 4} concentrations were also examined using the bulk Richardson number (R{sub B}) as a stability indicator. Four groups were distinguished: unstable cases, situations with pure shear flow, transitional stages and drainage flows. The highest contrast in mean CH{sub 4} concentrations between lower and upper heights was obtained for the transition and drainage cases, mainly associated to high concentrations from nearby sources. The impact of long range transport was analysed by means of 3-day isobaric backward air mass trajectories, which were calculated taking into account origins from Europe, Africa, the Atlantic Ocean and Local conditions. Assessment of the results showed the influence of S and SE wind sectors, especially with Local conditions associated with low winds. Finally, an estimation of the background CH{sub 4} concentration in the study period provided an

Intermolecular interactions involving C-H bonds, 3, Structure and energetics of the interaction between CH{sub 4} and CN{sup {minus}}

Energy Technology Data Exchange (ETDEWEB)

Novoa, J.J.; Whangbo, Myung-Hwan [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry; Williams, J.M. [Argonne National Lab., IL (United States)

1991-12-31

On the basis of SCF and single reference MP2 calculations, the full potential energy surface of the interaction between CH{sub 4} and CN{sup {minus}} was studied using extended basis sets of up to near Hartree-Fock limit quality. Colinear arrangements C-N{sup {minus}}{hor_ellipsis}H-CH{sub 3} and N-C{sup {minus}}{hor_ellipsis}H-CH{sub 3} are found to be the only two energy minima. The binding energies of these two structures are calculated to be 2.5 and 2.1 kcal/mol, respectively, at the MP2 level. The full vibrational analyses of two structures show a red shift of about 30 cm{sup {minus}1} for the v{sub s} C-H stretching.

Optical properties of bias-induced CH sub 4 -H sub 2 plasma for diamond film deposition

CERN Document Server

Zhu, X D; Zhou, H Y; Wen, X H; Li, D

2002-01-01

Methane (CH sub 4) and hydrogen (H sub 2) reactive gas mixture has been in situ investigated in a hot filament diamond chemical vapor deposition reactor with a negatively variable biasing voltage applied to the hot filament with respect to the substrate using infrared absorption spectroscopy and optical emission spectroscopy. It is found that CH sub 4 converts increasingly to C sub 2 H sub 2 upon raising the filament temperature in a pure thermal activation state, no optical emission of species is observed. Upon bias application, both CH sub 4 and C sub 2 H sub 2 in infrared (IR) absorption intensity decrease with increasing bias current, even the IR absorption intensity of C sub 2 H sub 2 decreases more rapidly than that of CH sub 4. Meanwhile, the clear emission lines indexed to H, CH, and CH sup + appear in the optical emission spectrum obtained, showing that a large amount of excited radicals are produced in the gas phase after applying bias. It is believed that the further generation of activated radical...

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

Science.gov (United States)

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.

CO2/CH4 Separation by a Mixed Matrix Membrane of Polymethylpentyne/MIL-53 Particles

Directory of Open Access Journals (Sweden)

Reza Abedini

2014-10-01

Full Text Available The effect of Materials Institute Lavoisier-53 (MIL-53 particles on gas transport properties of polymethylpentyne (PMP was investigated. MIL-53 was added to the polymer matrix with different loadings of 10, 20 and 30 wt%. The properties of MIL-53 and prepared membranes were analyzed through FTIR, SEM and TGA methods. The adsorption of CO2 and CH4 was conducted and analyzed accurately through Langmuir equation to investigate the gas transport properties of membranes. The results from TGA showed that degradation temperature (Td increases significantly with increasing MIL-53 loading. SEM images demonstrated that MIL-53 particles dispersed well in polymer matrix with no considerable agglomeration and no non-selective void formation at polymer/filler interface. In addition, CO2 and CH4 permeability measurement along with calculation of CO2/CH4 selectivity were performed. The results showed that the permeability of gases (especially for CO2 increased significantly by increasing the MIL-53 loading. Additionally, CO2/CH4 selectivity showed an increasing trend with increasing the MIL-53 weight percent. Unlike CH4, the CO2 solubility coefficient increased with increasing the MIL-53 loading because of high free volume of membrane and selective adsorption of CO2 with MIL-53. Despite CO2 solubility enhancement its diffusivity coefficient remained more or less unchanged. The enhancement in CH4 permeability has been mainly attributed to its slight incremental diffusivity due to the membrane's increasingly higher free volume. Finally, a comparison between membranes performance and CO2/CH4 Robeson upper bound showed that, the performance of membranes improved due to the presence of MIL-53 which was very close to the Robeson bound.

Bioelectrochemical methane (CH4) production in anaerobic digestion at different supplemental voltages.

Science.gov (United States)

Choi, Kwang-Soon; Kondaveeti, Sanath; Min, Booki

2017-12-01

Microbial electrolysis cells (MECs) at various cell voltages (0.5, 0.7 1.0 and 1.5V) were operated in anaerobic fermentation. During the start-up period, the cathode potential decreased from -0.63 to -1.01V, and CH 4 generation increased from 168 to 199ml. At an applied voltage of 1.0V, the highest methane yields of 408.3ml CH 4 /g COD glucose was obtained, which was 30.3% higher than in the control tests (313.4ml CH 4 /g COD glucose). The average current of 5.1mA was generated at 1.0V at which the maximum methane yield was obtained. The other average currents were 1.42, 3.02, 0.53mA at 0.5, 0.7, and 1.5V, respectively. Cyclic voltammetry and EIS analysis revealed that enhanced reduction currents were present at all cell voltages with biocatalyzed cathode electrodes (no reduction without biofilm), and the highest value was obtained with 1V external voltage. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fluxes of CH4 and N2O in aspen stands grown under ambient and twice-ambient CO2

DEFF Research Database (Denmark)

Ambus, P.; Robertson, G.P.

1999-01-01

Elevated atmospheric CO2 has the potential to change below-ground nutrient cycling and thereby alter the soil-atmosphere exchange of biogenic trace gases. We measured fluxes of CH4 and N2O in trembling aspen (Populus tremuloides Michx.) stands grown in open-top chambers under ambient and twice......-ambient CO2 concentrations crossed with `high' and low soil-N conditions. Flux measurements with small static chambers indicated net CH4 oxidation in the open-top chambers. Across dates, CH4 oxidation activity was significantly (P CO2 (8.7 mu g CH4-C m(-2) h(-1)) than...... with elevated CO2 (6.5 mu g CH4-C m(-2) h(-1)) in the low N soil. Likewise, across dates and soil N treatments CH4 was oxidized more rapidly (P CO2 (9.5 mu g CH4-C m(-2) h(-1)) than in chambers with elevated CO2 (8.8 mu g CH4-C m(-2) h(-1)). Methane oxidation in soils incubated...

Ionic fragmentation following core-level photoionization of Sn(CH3)4 by soft X-rays

International Nuclear Information System (INIS)

Ueda, Kiyoshi; Shigemasa, Eiji; Sato, Yukinori; Yagishita, Akira; Hayaishi, Tatsuji

1990-01-01

Ionic fragmentation following the photoionization of Sn(CH 3 ) 4 (TMT) has been studied in the photon energy range of 60-600 eV using synchrotron radiation and time-of-flight mass spectrometry. Each of the Sn:4d, 4p, 3d and C:1s photoionization leads to a type of ionic fragmentation that is characteristic of each ionized core. The Sn:4d photoionization above 60 eV predominantly produces the doubly-charged TMT which dissociates into two singly-charged ions and some neutral fragments. The ions produced in this pathway are CH 3 + , C 2 H 3 + , C 2 H 5 + , SnCH m + and/or Sn + . The Sn:4p photoionization produces the triply-charged TMT and enhances the production of H + , CHsub(m' + ) (m' = 0-3) and Sn + significantly. The Sn:3d photoionization produces multiply-charged TMT whose charges are 3-5 and enhances the production of H + , CHsub(m' + ) (m' = 0-2) and Sn + significantly. The C:1s photoionization produces doubly-charged TMT via the KVV Auger transition and enhances the production of CH 3 + , C 2 H 3 + , SnCH m + and/or Sn + . (orig.)

Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates

Science.gov (United States)

Saad Khan, Muhammad; Yaqub, Sana; Manner, Naathiya; Ani Karthwathi, Nur; Qasim, Ali; Mellon, Nurhayati Binti; Lal, Bhajan

2018-04-01

Clathrate hydrates are eminent structures regard as a threat to the gas and oil industry in light of their irritating propensity to subsea pipelines. For natural gas transmission and processing, the formation of gas hydrate is one of the main flow assurance delinquent has led researchers toward conducting fresh and meticulous studies on various aspects of gas hydrates. This paper highlighted the thermodynamic analysis on pure CH4 and CO2 gas hydrates on the custom fabricated equipment (Sapphire cell hydrate reactor) for experimental validation. CO2 gas hydrate formed at lower pressure (41 bar) as compared to CH4 gas hydrate (70 bar) while comparison of thermodynamic properties between CH4 and CO2 also presented in this study. This preliminary study could provide pathways for the quest of potent hydrate inhibitors.

Study of the daily and seasonal atmospheric CH4 mixing ratio variability in a rural Spanish region using 222Rn tracer

Science.gov (United States)

Grossi, Claudia; Vogel, Felix R.; Curcoll, Roger; Àgueda, Alba; Vargas, Arturo; Rodó, Xavier; Morguí, Josep-Anton

2018-04-01

The ClimaDat station at Gredos (GIC3) has been continuously measuring atmospheric (dry air) mixing ratios of carbon dioxide (CO2) and methane (CH4), as well as meteorological parameters, since November 2012. In this study we investigate the atmospheric variability of CH4 mixing ratios between 2013 and 2015 at GIC3 with the help of co-located observations of 222Rn concentrations, modelled 222Rn fluxes and modelled planetary boundary layer heights (PBLHs). Both daily and seasonal changes in atmospheric CH4 can be better understood with the help of atmospheric concentrations of 222Rn (and the corresponding fluxes). On a daily timescale, the variation in the PBLH is the main driver for 222Rn and CH4 variability while, on monthly timescales, their atmospheric variability seems to depend on emission changes. To understand (changing) CH4 emissions, nocturnal fluxes of CH4 were estimated using two methods: the radon tracer method (RTM) and a method based on the EDGARv4.2 bottom-up emission inventory, both using FLEXPARTv9.0.2 footprints. The mean value of RTM-based methane fluxes (FR_CH4) is 0.11 mg CH4 m-2 h-1 with a standard deviation of 0.09 or 0.29 mg CH4 m-2 h-1 with a standard deviation of 0.23 mg CH4 m-2 h-1 when using a rescaled 222Rn map (FR_CH4_rescale). For our observational period, the mean value of methane fluxes based on the bottom-up inventory (FE_CH4) is 0.33 mg CH4 m-2 h-1 with a standard deviation of 0.08 mg CH4 m-2 h-1. Monthly CH4 fluxes based on RTM (both FR_CH4 and FR_CH4_rescale) show a seasonality which is not observed for monthly FE_CH4 fluxes. During January-May, RTM-based CH4 fluxes present mean values 25 % lower than during June-December. This seasonal increase in methane fluxes calculated by RTM for the GIC3 area appears to coincide with the arrival of transhumant livestock at GIC3 in the second half of the year.

BOREAS TGB-1 Soil CH4 and CO2 Profile Data from NSA Tower Sites

Science.gov (United States)

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

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 methane (CH4) and carbon dioxide (CO2) concentrations in soil profiles from the NSA-OJP, NSA-OBS, NSA-YJP, and NSA-BP sites during the period of 23-May to 20-Sep-1994. The soil gas sampling profiles of CH 4 and CO 2 were completed to quantify controls on CO2 and CH4 fluxes in the boreal forest. The data are provided in tabular ASCII files.

A Switchable Molecular Dielectric with Two Sequential Reversible Phase Transitions: [(CH3)4P]4[Mn(SCN)6].

Science.gov (United States)

Li, Qiang; Shi, Ping-Ping; Ye, Qiong; Wang, Hui-Ting; Wu, De-Hong; Ye, Heng-Yun; Fu, Da-Wei; Zhang, Yi

2015-11-16

A new organic-inorganic hybrid switchable and tunable dielectric compound, [(CH3)4P]4[Mn(SCN)6] (1), exhibits three distinct dielectric states above room temperature and undergoes two reversible solid-state phase transitions, including a structural phase transition at 330 K and a ferroelastic phase transition with the Aizu notation of mmmF2/m at 352 K. The variable-temperature structural analyses disclose that the origin of the phase transitions and dielectric anomalies can be ascribed to the reorientation or motion of both the [(CH3)4P](+) cations and [Mn(SCN)6](4-) anions in solid-state crystals.

In-situ studies of microbial CH{sub 4} oxidation efficiency in Arctic wetland soils. Applications of stable carbon isotopes

Energy Technology Data Exchange (ETDEWEB)

Preuss, Inken-Marie

2013-07-05

Arctic wetland soils are significant sources of the climate-relevant trace gas methane (CH{sub 4}). The observed accelerated warming of the Arctic is expected to cause deeper permafrost thawing followed by increased carbon mineralization and CH{sub 4} formation in water-saturated permafrost-affected tundra soils thus creating a positive feedback to climate change. Aerobic CH{sub 4} oxidation is regarded as the key process reducing CH{sub 4} emissions from wetlands, but quantification of turnover rates has remained difficult so far. This study improved the in-situ quantification of microbial CH{sub 4} oxidation efficiency in arctic wetland soils in Russia's Lena River Delta based on stable isotope signatures of CH{sub 4}. In addition to the common practice of determining the stable isotope fractionation during oxidation, additionally the fractionation effect of diffusion, an important gas transport mechanism in tundra soils, was investigated for both saturated and unsaturated conditions. The isotopic fractionation factors α{sub ox} and α{sub diff} were used to calculate the CH{sub 4} oxidation efficiency from the CH{sub 4} stable isotope signatures of wet polygonal tundra soils of different hydrology. Further, the method was used to study the short-term effects of temperature increase with a climate manipulation experiment. For the first time, the stable isotope fractionation of CH{sub 4} diffusion through water-saturated soils was determined with α{sub diff} = 1.001 ± 0.0002 (n = 3). CH{sub 4} stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was α{sub diff} = 1.013 ± 0.003 (n = 18). For the studied sites the fractionation factor for diffusion under saturated conditions α{sub diff} = 1.001 seems to be of utmost importance for the quantification of the CH{sub 4} oxidation efficiency, since most of the CH{sub 4} is oxidized in the saturated part at the aerobic-anaerobic interface. Furthermore

Numerical Simulation and Industrial Experimental Research on the Coherent Jet with "CH4 + N2" Mixed Fuel Gas

Science.gov (United States)

Hu, Shaoyan; Zhu, Rong; Dong, Kai; Liu, Runzao

2018-06-01

Coherent jet technology is widely used in the electric arc furnace (EAF) steelmaking process to deliver more energy and momentum into the molten steel bath. Meanwhile, the characteristics of a coherent jet using pure CH4 as the fuel gas have been well investigated in previous studies. To reduce the consumption of CH4, coherent jet technology using "CH4 + N2" mixed fuel gas instead of pure CH4 was proposed and studied in detail by numerical simulation in the present work. The Eddy Dissipation Concept model, which has detailed chemical kinetic mechanisms, was adopted to model the fuel gas combustion reactions. Experimental measurements were carried out to validate the accuracy of the computational model. The present study shows that the jet characteristics of the main oxygen improve along with the increase of the CH4 ratio in fuel gas and with the increase of the flow rate of fuel gas. When the CH4 ratio in the fuel gas is 25 pct, the fuel gas flow rate only has a limited influence on the jet characteristics, unlike the rest of the fuel gas compositions, because a high N2 proportion deteriorates the combustion performance and leads to severe incomplete combustion. Moreover, a false potential core phenomenon was observed and explained in the present study. Based on the average values, the jet length of a coherent jet with 75 pct CH4 can achieve 89.8 pct of that with 100 pct CH4. Finally, an industrial experiment was carried out on a commercial 100t EAF using coherent jet with 75 pct CH4, showing that the average CH4 consumption was reduced from 3.84 to 3.05 Nm3 t-1 under the premise of no obvious changes in the other production indexes.

Synthesis of fluorinated ReCl(4,4'-R2-2,2'-bipyridine)(CO)3 complexes and their photophysical characterization in CH3CN and supercritical CO2.

Science.gov (United States)

Doherty, Mark D; Grills, David C; Fujita, Etsuko

2009-03-02

Two new CO(2)-soluble rhenium(I) bipyridine complexes bearing the fluorinated alkyl ligands 4,4'-(C(6)F(13)CH(2)CH(2)CH(2))(2)-2,2'-bipyridine (1a), and 4,4'-(C(8)F(17)CH(2)CH(2)CH(2))(2)-2,2'-bipyridine (1b) have been prepared and their photophysical properties investigated in CH(3)CN and supercritical CO(2). Electrochemical and spectroscopic characterization of these complexes in CH(3)CN suggests that the three methylene units effectively insulate the bipyridyl rings and the rhenium center from the electron-withdrawing effect of the fluorinated alkyl chains. Reductive quenching of the metal-to-ligand charge-transfer excited states with triethylamine reveals quenching rate constants in supercritical CO(2) that are only 6 times slower than those in CH(3)CN.

Synthesis and crystal structure of 4-fluorobenzylammonium dihydrogen phosphate, [FC6H4CH2NH3]H2PO4

Directory of Open Access Journals (Sweden)

Ali Rayes

2016-12-01

Full Text Available The asymmetric unit of the title salt, [p-FC6H4CH2NH3]+·H2PO4−, contains one 4-fluorobenzylammonium cation and one dihydrogen phosphate anion. In the crystal, the H2PO4− anions are linked by O—H...O hydrogen bonds to build corrugated layers extending parallel to the ab plane. The FC6H4CH2NH3+ cations lie between these anionic layers to maximize the electrostatic interactions and are linked to the H2PO4− anions through N—H...O hydrogen bonds, forming a three-dimensional supramolecular network. Two hydrogen atoms belonging to the dihydrogen phosphate anion are statistically occupied due to disorder along the OH...HO direction.

Dentritic Carbosilanes Containing Silicon-Bonded 1-[C6H2(CH2NMe2)2-3,5-Li-4] or 1-[C6H3(CH2NMe2)-4-Li-3] Mono-and Bis(amino)aryllithium End Groups: Structure of {[CH2SiMe2C6H3(CH2NMe2)-4-Li-3]2}2

NARCIS (Netherlands)

Koten, G. van; Kleij, A.W.; Kleijn, H.; Jastrzebski, J.T.B.H.; Smeets, W.J.J.; Spek, A.L.

1999-01-01

A useful synthetic procedure for the incorporation of the potentially multidentate monoanionic 1-[C6H2(CH2NMe2)2-3,5]- (=NCN) and 1-[C6H3(CH2NMe2)-4]- (=CN) ligands via the para-position on the periphery of carbosilane (CS) dendrimers has been developed. Lithiation of suitable brominated precursors

Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

Science.gov (United States)

Zhou, Yong; Zhang, Dong H

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

Kinetics of the Formation and Dissociation of Gas Hydrates from CO₂-CH₄ Mixtures

Directory of Open Access Journals (Sweden)

Devinder Mahajan

2012-07-01

Full Text Available Sequestration of carbon dioxide (CO₂ in the form of its hydrates in natural methane (CH₄ hydrate reservoirs, via CO₂/CH₄ exchange, is an attractive pathway that also yields valuable CH₄ gas as product. In this paper, we describe a macroscale experiment to form CO₂ and CH₄-CO₂ hydrates, under seafloor-mimic conditions, in a vessel fitted with glass windows that provides visualization of hydrates throughout formation and dissociation processes. Time resolved pressure and temperature data as well as images of hydrates are presented. Quantitative gas conversions with pure CO₂, calculated from gas chromatographic measurements yielded values that range from 23 – 59% that correspond to the extent of formed hydrates. In CH₄-rich CH₄-CO₂ mixed gas systems, CH₄ hydrates were found to form preferentially.

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

Science.gov (United States)

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

Assessing fugitive emissions of CH4 from high-pressure gas pipelines in the UK

Science.gov (United States)

Clancy, S.; Worrall, F.; Davies, R. J.; Almond, S.; Boothroyd, I.

2016-12-01

Concern over the greenhouse gas impact of the exploitation of unconventional natural gas from shale deposits has caused a spotlight to be shone on to the entire hydrocarbon industry. Numerous studies have developed life-cycle emissions inventories to assess the impact that hydraulic fracturing has upon greenhouse gas emissions. Incorporated within life-cycle assessments are transmission and distribution losses, including infrastructure such as pipelines and compressor stations that pressurise natural gas for transport along pipelines. Estimates of fugitive emissions from transmission, storage and distribution have been criticized for reliance on old data from inappropriate sources (1970s Russian gas pipelines). In this study, we investigate fugitive emissions of CH4 from the UK high pressure national transmission system. The study took two approaches. Firstly, CH4 concentration is detected by driving along roads bisecting high pressure gas pipelines and also along an equivalent distance along a route where no high pressure gas pipeline was nearby. Five pipelines and five equivalent control routes were driven and the test was that CH4 measurements, when adjusted for distance and wind speed, should be greater on any route with a pipe than any route without a pipe. Secondly, 5 km of a high pressure gas pipeline and 5 km of equivalent farmland, were walked and soil gas (above the pipeline where present) was analysed every 7 m 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

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

Science.gov (United States)

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

We use the GEOS-Chem global 3-D model of atmospheric chemistry and transport and an ensemble Kalman filter to simultaneously infer regional fluxes of methane (CH4) and carbon dioxide (CO2) directly from GOSAT retrievals of XCH4 : XCO2, using sparse ground-based CH4 and CO2 mole fraction data to anchor the ratio. This work builds on the previously reported theory that takes into account that (1) these ratios are less prone to systematic error than either the full-physics data products or the proxy CH4 data products; and (2) the resulting CH4 and CO2 fluxes are self-consistent. We show that a posteriori fluxes inferred from the GOSAT data generally outperform the fluxes inferred only from in situ data, as expected. GOSAT CH4 and CO2 fluxes are consistent with global growth rates for CO2 and CH4 reported by NOAA and have a range of independent data including new profile measurements (0-7 km) over the Amazon Basin that were collected specifically to help validate GOSAT over this geographical region. We find that large-scale multi-year annual a posteriori CO2 fluxes inferred from GOSAT data are similar to those inferred from the in situ surface data but with smaller uncertainties, particularly over the tropics. GOSAT data are consistent with smaller peak-to-peak seasonal amplitudes of CO2 than either the a priori or in situ inversion, particularly over the tropics and the southern extratropics. Over the northern extratropics, GOSAT data show larger uptake than the a priori but less than the in situ inversion, resulting in small net emissions over the year. We also find evidence that the carbon balance of tropical South America was perturbed following the droughts of 2010 and 2012 with net annual fluxes not returning to an approximate annual balance until 2013. In contrast, GOSAT data significantly changed the a priori spatial distribution of CH4 emission with a 40 % increase over tropical South America and tropical Asia and a smaller decrease over Eurasia and temperate

Renewable energy based catalytic CH4 conversion to fuels

NARCIS (Netherlands)

Baltrusaitis, Jonas; Jansen, I.; Schuttlefield, J.D.S.

2014-01-01

Natural gas is envisioned as a primary source of hydrocarbons in the foreseeable future. With the abundance of shale gas, the main concerns have shifted from the limited hydrocarbon availability to the sustainable methods of CH4 conversion to fuels. This is necessitated by high costs of natural gas

Release of CO{sub 2} and CH{sub 4} from small wetland lakes in western Siberia

Energy Technology Data Exchange (ETDEWEB)

Repo, M.E.; Huttunen, J.T.; Martikainen, P.J. [Univ. of Kuopio, Dept. of Env ironmental Science, FI-70211 Kuopio (Finland); Naumov, A.V.; Chichulin, A.V. [I nst. of Soil Science and Agrochemistry, Russian Academy of Science, 630099 Novos ibirsk (Russian Federation); Lapshina, E.D. [Yugra State Univ., 628012, Khanty-Mansiysk (Russian Federation); Bleuten , W. [Utrecht Univ., Dept. of Physical Geography,3508 TC Utrecht (Netherlands)

2007-11-15

CO{sub 2} and CH{sub 4} fluxes were measured from three small wetland lakes located in the middle taiga and forest tundra zones on West Siberian Lowlands (WSL), the world's largest wetland area. Fluxes were measured during summer 2005 using floating chambers and were validated against the thin boundary layer model based on the relationship between gas exchange and wind speed. All studied lakes were supersaturated with CO{sub 2} and CH{sub 4}, and acted on a seasonal basis as sources of these greenhouse gases to the atmosphere. Daily mean CO{sub 2} fluxes measured with chambers ranged from near the zero to 3.1 g CO{sub 2}/m{sup 2}/d and corresponding CH{sub 4} fluxes from 1.1 to 120 mg CH{sub 4}/m{sup 2}/d. CH{sub 4} ebullition (0.65-11 mg CH{sub 4}/m{sup 2}/d) was detected in two of the lakes. Total carbon evasion from the studied lakes during the active season was 23-66 g C/m{sup 2}, of which more than 90% was released as CO{sub 2}-C. The carbon loss per unit area from the studied lakes was of similar magnitude as previously reported values of net carbon uptake of Siberian peatlands. This emphasizes the importance of small water-bodies in the carbon balance of West Siberian landscape.

CO2 and CH4 fluxes in a Spartina salt marsh and brackish Phragmites marsh in Massachusetts

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Tang, J.; Wang, F.; Kroeger, K. D.; Gonneea, M. E.

2017-12-01

Coastal salt marshes play an important role in global and regional carbon cycling. Tidally restricted marshes reduce salinity and provide a habitat suitable for Phragmites invasion. We measured greenhouse gas (GHG) emissions (CO2 and CH4) continuously with the eddy covariance method and biweekly with the static chamber method in a Spartina salt marsh and a Phragmites marsh on Cape Cod, Massachusetts, USA. We did not find significant difference in CO2 fluxes between the two sites, but the CH4 fluxes were much higher in the Phragmites site than the Spartina marsh. Temporally, tidal cycles influence the CO2 and CH4 fluxes in both sites. We found that the salt marsh was a significant carbon sink when CO2 and CH4 fluxes were combined. Restoring tidally restricted marshes will significantly reduce CH4 emissions and provide a strong ecosystem carbon service.

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

Science.gov (United States)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Preparation of CH4 for 14C measurements

International Nuclear Information System (INIS)

Cechova, A.; Grgula, M.; Povinec, P.; Sivo, A.

1988-01-01

An improved method of methane preparation from wood samples is described. It consists of the preparation of α-cellulose to secure a complete removal of contamination from the wood, its combustion to the form of CO 2 and the preparation of CH 4 in a new designed hydrogenation converter. Purified methane is suitable as a gas filling of the proportional counter. (author). 1 fig., 16 ref

Direct measurements of methoxy removal rate constants for collisions with CH4, Ar, N2, Xe, and CF4 in the temperature range 673--973K

International Nuclear Information System (INIS)

Wantuck, P.J.; Oldenborg, R.C.; Baugchum, S.L.; Winn, K.R.

1988-01-01

Removal rate constants for CH 3 O by CH 4 , Ar, N 2 , Xe, and CF 4 were measured over a 400K temperature range using a laser photolysis/laser-induced fluorescence technique. Rapid methoxy removal rates are observed for the non-reactive collision partners (Ar, N 2 , Xe, and CF 4 ) at elevated temperatures showing that the dissociation and isomerization channels for CH 3 O are indeed important. The total removal rate constant (reaction /plus/ dissociation and/or isomerization) for CH 4 exhibits a linear dependence on temperature and has a removal rate constant, k/sub r/ /equals/ (1.2 +- 0.6) /times/ 10/sup /minus/8/exp[(/minus/101070 +- 350)/T]cm 3 molecule/sup /minus/1/s/sup /minus/1/. Assuming that the removal rate constant due to dissociation and/or isomerization are similar for CH 4 and CF 4 , the reaction rate constant for CH 3 O /plus/ CH 4 is equal to (1.7 +- 1.0) /times/ 10/sup /minus/10/exp[(/minus/7480 +- 1100)/T]cm 3 molecule/sup /minus/1/s/sup /minus/1/. 7 refs., 4 figs

Atmospheric modeling of Mars CH4 subsurface clathrates releases mimicking SAM and 2003 Earth-based detections

Science.gov (United States)

Pla-García, J.; Rafkin, S. C.

2017-12-01

The aim of this work is to establish the amount of mixing during all martian seasons to test whether CH4 releases inside or outside of Gale crater are consistent with MSL-SAM observations. Several modeling scenarios were configured, including instantaneous and steady releases, both inside and outside the crater. A simulation to mimic the 2003 Earth-based detections (Mumma et al. 2009 or M09) was also performed. In the instantaneous release inside Gale experiments, Ls270 was shown to be the faster mixing season when air within and outside the crater was well mixed: all tracer mass inside the crater is diluted after just 8 hours. The mixing of near surface crater air with the external environment in the rest of the year is potentially rapid but slower than Ls270.In the instantaneous release outside Gale (NW) experiment, in just 12 hours the CH4 that makes it to the MSL landing location is diluted by six orders of magnitude. The timescale of mixing in MRAMS experiments is on the order of 1 sol regardless of season. The duration of the CH4 peak observed by SAM is 100 sols. Therefore there is a steady release inside the crater, or there is a very large magnitude steady release outside the crater. In the steady release Gale experiments, CH4 flux rate from ground is 1.8 kg m-2 s-1 (derived from Gloesener et al. 2017 clathrates fluxes) and it is not predictive. In these experiments, 200 times lower CH4 values detected by SAM are modeled around MSL location. There are CH4 concentration variations of orders of magnitude depending on the hour, so timing of SAM measurements is important. With a larger (but further away) outside crater release area compared to inside, similar CH4 values around MSL are modeled, so distance to source is important. In the steady experiments mimicking M09 detection release area, only 12 times lower CH4 values detected by SAM are modeled around MSL. The highest value in the M09 modeled scenario (0.6 ppbv) is reached in Ls270. This value is the

The c2d Spitzer spectroscopic survey of ices around low-mass young stellar objects. III. CH4

NARCIS (Netherlands)

Oberg, Karin I.; Boogert, A. C. Adwin; Pontoppidan, Klaus M.; Blake, Geoffrey A.; Evans, Neal J.; Lahuis, Fred; van Dishoeck, Ewine F.

2008-01-01

CH4 is proposed to be the starting point of a rich organic chemistry. Solid CH4 abundances have previously been determined mostly toward high-mass star-forming regions. Spitzer IRS now provides a unique opportunity to probe solid CH4 toward low-mass star-forming regions as well. Infrared spectra

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

Science.gov (United States)

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

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

Science.gov (United States)

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

Study of the properties of plasma of CH4/H2 and its interactions with liquid hydrocarbons

International Nuclear Information System (INIS)

Gambus, G.; Patino, P.

2003-01-01

Properties of a CH 4 /H 2 plasma, as a reducing agent in heterogeneous reactions with one olefin hydrocarbon, were studied in this work. The characterization of the plasma was carried out by means of optical emission spectroscopy, by varying the gas composition (CH 4 /H 2 ) and the working pressure, in a radio frequency discharge. The variation of the relative populations of H and CH radicals was followed, at pressures between 0.001 and 0.4 mbar and CH 4 /H 2 proportions 1:1 to 1:5. The conditions selected for treating squalene were 0.1 mbar and CH 4 /H 2 of 1:5. Although these conditions did not yield the maximum intensities for the two signals, these were strong enough and black carbon and polymers ceased from being produced under this regime. At 5 C, more than two double bonds per molecule, out of six, were hydrogenated with the plasma in 12 hours. (Author)

Observation of CH4 and other Non-CO2 Green House Gas Emissions from California

Energy Technology Data Exchange (ETDEWEB)

Fischer, Marc L.; Zhao, Chuanfeng; Riley, William J.; Andrews, Arlyn C.

2009-01-09

In 2006, California passed the landmark assembly bill AB-32 to reduce California's emissions of greenhouse gases (GHGs) that contribute to global climate change. AB-32 commits California to reduce total GHG emissions to 1990 levels by 2020, a reduction of 25 percent from current levels. To verify that GHG emission reductions are actually taking place, it will be necessary to measure emissions. We describe atmospheric inverse model estimates of GHG emissions obtained from the California Greenhouse Gas Emissions Measurement (CALGEM) project. In collaboration with NOAA, we are measuring the dominant long-lived GHGs at two tall-towers in central California. Here, we present estimates of CH{sub 4} emissions obtained by statistical comparison of measured and predicted atmospheric mixing ratios. The predicted mixing ratios are calculated using spatially resolved a priori CH{sub 4} emissions and surface footprints, that provide a proportional relationship between the surface emissions and the mixing ratio signal at tower locations. The footprints are computed using the Weather Research and Forecast (WRF) coupled to the Stochastic Time-Inverted Lagrangian Transport (STILT) model. Integral to the inverse estimates, we perform a quantitative analysis of errors in atmospheric transport and other factors to provide quantitative uncertainties in estimated emissions. Regressions of modeled and measured mixing ratios suggest that total CH{sub 4} emissions are within 25% of the inventory estimates. A Bayesian source sector analysis obtains posterior scaling factors for CH{sub 4} emissions, indicating that emissions from several of the sources (e.g., landfills, natural gas use, petroleum production, crops, and wetlands) are roughly consistent with inventory estimates, but livestock emissions are significantly higher than the inventory. A Bayesian 'region' analysis is used to identify spatial variations in CH{sub 4} emissions from 13 sub-regions within California

Contribution of rice straw carbon to CH4 emission from rice paddies using 13C-enriched rice straw

Science.gov (United States)

Watanabe, Akira; Yoshida, Mariko; Kimura, Makoto

1998-04-01

It is generally recognized that the application of rice straw (RS) increases CH4 emission from rice paddies. To estimate the contribution of RS carbon to CH4 emission, a pot experiment was conducted using 13C-enriched RS. The percentage contributions of RS carbon to CH4 emission throughout the rice growth period were 10±1, 32±3, and 43±3% for the treatments with RS applied at the rates of 2, 4, and 6 g kg-1 soil, respectively. The increase in the rate of application of RS increased CH4 emission derived from both RS carbon and other carbon sources. The percentage contribution of RS carbon to CH4 emission was larger in the earlier period (maximum 96%) when the decomposition rate of RS was larger. After RS decomposition had slowed, CH4 emission derived from RS carbon decreased. However, the δ13C values of CH4 emitted from the pots with 13C-enriched RS applied at rates of 4 and 6 g kg-1 soil were significantly higher than those from the pots with natural RS until the harvesting stage. An increased atom-13C% of roots of rice plants growing in the pots with 6 g kg-1 of 13C-enriched RS at around the maximum tiller number stage and a decrease during the following 2 months suggested that rice plants assimilated RS carbon once and then released a portion of it. This supply of RS carbon from roots may be one of the sources of CH4 in the late period of rice growth.

Study of atmospheric CH4 mole fractions at three WMO/GAW stations in China

Science.gov (United States)

Fang, Shuang-Xi; Zhou, Ling-Xi; Masarie, Kenneth A.; Xu, Lin; Rella, Chris W.

2013-05-01

CH4 mole fractions were continuously measured from 2009 to 2011 at three WMO/GAW stations in China (Lin'an, LAN; Longfengshan, LFS; and Waliguan, WLG) using three Cavity Ring Down Spectroscopy instruments. LAN and LFS are GAW regional measurement stations. LAN is located in China's most economically developed region, and LFS is in a rice production area (planting area > 40,000 km2). WLG is a global measurement station in remote northwest China. At LAN, high methane mole fractions are observed in all seasons. Surface winds from the northeast enhance CH4 values, with a maximum increase of 32 ± 15 ppb in summer. The peak to peak amplitude of the seasonal cycle is 77 ± 35 ppb. At LFS, the diurnal cycle amplitude is approximately constant throughout the year except summer, when a value of 196 ± 65 ppb is observed. CH4 values at LFS reach their peak in July, which is different from seasonal variations typically observed in the northern hemisphere. CH4 mole fractions at WLG show both the smallest values and the lowest variability. Maximum values occur during summer, which is different from other northern hemisphere WMO/GAW global stations. The seasonal cycle amplitude is 17 ± 11 ppb. The linear growth rates at LAN, LFS, and WLG are 8.0 ± 1.2, 7.9 ± 0.9, and 9.4 ± 0.2 ppb yr-1, respectively, which are all larger than the global mean over the same 3 year period. Results from this study attempt to improve our basic understanding of observed atmospheric CH4 in China.

SYNTHESIS OF NEW BIS(CYCLOPENTADIENYL)YTTRIUM COMPLEXES WITH ETHER FUNCTIONALIZED CYCLOPENTADIENYL LIGANDS - CRYSTAL-STRUCTURE OF [(C(5)H(4)CH(2)CH(2)OME)(2)Y(MU-H)(2)BH2

NARCIS (Netherlands)

LASKE, DA; DUCHATEAU, R; TEUBEN, JH; SPEK, AL

1993-01-01

Treatment of C(5)H(4)CH(2)CH(2)OMe.Li(TMEDA) (TMEDA = N, N, N', N' tetramethylethylenediamine) with half an equivalent of YCl3(THF)(3.5) in toluene afforded the salt- and solvent-free dimeric biscyclopentadienyl yttrium chloride [(C(5)H(4)CH(2)CH(2)OMe)(2)Y-(mu-Cl)](2) (1). Reaction of 1 with one

Comprehensive effects of a sedge plant on CH4 and N2O emissions in an estuarine marsh

Science.gov (United States)

Li, Yangjie; Wang, Dongqi; Chen, Zhenlou; Hu, Hong

2018-05-01

Although there have been numerous studies focusing on plants' roles in methane (CH4) emissions, the influencing mechanism of wetland plants on nitrous oxide (N2O) emissions has rarely been studied. Here, we test whether wetland plants also play an important role in N2O emissions. Gas fluxes were determined using the in situ static flux chamber technique. We also carried out pore-water extractions, sedge removal experiments and tests of N2O transportation. The brackish marsh acted as a net source of both CH4 and N2O. However, sedge plants played the opposite role in CH4 and N2O emissions. The removal of the sedges led to reduced CH4 emissions and increased accumulation of CH4 inside the sediment. Apart from being a conduit for CH4 transport, the sedges made a greater contribution to CH4 oxidation than CH4 production. The sedges exerted inhibitory effects on the release of N2O. The N2O was barely detectable inside the sediment in both vegetated and vegetation-removed plots. The denitrification measurements and nitrogen addition (the addition rates were equal to 0.028, 0.056 and 0.112 g m-2) experiments suggest that denitrification associated with N2O production occurred mainly in the surface sediment layer. The vascular sedge could transport atmospheric N2O downward into the rhizosphere. The rhizospheric sediment, together with the vascular sedge, became an effective sink of atmospheric N2O.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Kinetics of the CH{sub 3} + HCl/DCl {sup {yields}} CH{sub 4}/CH{sub 3}D + Cl and CD{sub 3} + HCl/DCl {sup {yields}} CD{sub 3}H/CD{sub 4} + Cl reactions: An experimental H atom tunneling investigation

Energy Technology Data Exchange (ETDEWEB)

Eskola, Arkke J. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014, University of Helsinki, Helsinki (Finland); Seetula, Jorma A. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014, University of Helsinki, Helsinki (Finland)], E-mail: seetula@csc.fi; Timonen, Raimo S. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014, University of Helsinki, Helsinki (Finland)

2006-12-11

The kinetics of the radical reactions of CH{sub 3} with HCl or DCl and CD{sub 3} with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH{sub 3} (or CD{sub 3}) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH{sub 3}COCH{sub 3} (or CD{sub 3}COCD{sub 3}). The decay of CH{sub 3}/CD{sub 3} was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH{sub 3} and CD{sub 3} reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (-E {sub a}/RT) (error limits stated are 1{sigma} + Students t values, units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 3} + HCl) = [1.004 + 85.64 exp (-0.02438 x T/K)] x (3.3 {+-} 1.3) x 10{sup -13} exp [-(4.8 {+-} 0.6) kJ mol{sup -1}/RT] and k(CD{sub 3} + HCl) = [1.002 + 73.31 exp (-0.02505 x T/K)] x (2.7 {+-} 1.2) x 10{sup -13} exp [-(3.5 {+-} 0.5) kJ mol{sup -1}/RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (-E {sub a}/RT) (error limits stated are 1{sigma} + Students t values, units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 3} + DCl) = (2.4 {+-} 1.6) x 10{sup -13} exp [-(7.8 {+-} 1.4) kJ mol{sup -1}/RT] and k(CD{sub 3} + DCl) = (1.2 {+-} 0.4) x 10{sup -13} exp [-(5.2 {+-} 0.2) kJ mol{sup -1}/RT] cm{sup 3} molecule{sup -1} s{sup -1}. Curvature in the Arrhenius plots of the H-atom abstraction reactions at low temperatures was analyzed by considering H-atom tunneling through the reaction barrier and primary kinetic isotope effect. Contribution of tunneling in it was concluded to be

In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

KAUST Repository

Al-Sabban, Bedour E.; Falivene, Laura; Kozlov, Sergey M.; Aguilar Tapia, Antonio; Ould-Chikh, Samy; Hazemann, Jean-Louis; Cavallo, Luigi; Basset, Jean-Marie; Takanabe, Kazuhiro

2017-01-01

Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals

Effects of Long-Term CO2 Enrichment on Soil-Atmosphere CH4 Fluxes and the Spatial Micro-Distribution of Methanotrophic Bacteria.

Science.gov (United States)

Karbin, Saeed; Guillet, Cécile; Kammann, Claudia I; Niklaus, Pascal A

2015-01-01

Effects of elevated atmospheric CO2 concentrations on plant growth and associated C cycling have intensively been studied, but less is known about effects on the fluxes of radiatively active trace gases other than CO2. Net soil-atmosphere CH4 fluxes are determined by the balance of soil microbially-driven methane (CH4) oxidation and methanogenesis, and both might change under elevated CO2. Here, we studied CH4 dynamics in a permanent grassland exposed to elevated CO2 for 14 years. Soil-atmosphere fluxes of CH4 were measured using large static chambers, over a period of four years. The ecosystem was a net sink for atmospheric CH4 for most of the time except summer to fall when net CH4 emissions occurred. We did not detect any elevated CO2 effects on CH4 fluxes, but emissions were difficult to quantify due to their discontinuous nature, most likely because of ebullition from the saturated zone. Potential methanotrophic activity, determined by incubation of fresh sieved soil under standardized conditions, also did not reveal any effect of the CO2 treatment. Finally, we determined the spatial micro-distribution of methanotrophic activity at less than 5× atmospheric (10 ppm) and elevated (10000 ppm) CH4 concentrations, using a novel auto-radiographic technique. These analyses indicated that domains of net CH4 assimilation were distributed throughout the analyzed top 15 cm of soils, with no dependence on CH4 concentration or CO2 treatment. Our investigations suggest that elevated CO2 exerts no or only minor effects on CH4 fluxes in the type of ecosystem we studied, at least as long as soil moisture differences are small or absent as was the case here. The autoradiographic analyses further indicate that the spatial niche of CH4 oxidation does not shift in response to CO2 enrichment or CH4 concentration, and that the same type of methanotrophs may oxidize CH4 from atmospheric and soil-internal sources.

Tidal influence on the sea-to-air transfer of CH4 in the coastal ocean

International Nuclear Information System (INIS)

Hahm, Doshik; Kim, Guebuem; Lee, Yong-Woo; Nam, Sungh-Yun; Kim, Kyung-Ryul; Kim, Kuh

2006-01-01

We obtained real-time monitoring data of water temperature, salinity, wind, current, CH 4 and other oceanographic parameters in a coastal bay in the southern sea of Korea from July 8 to August 15, 2003, using an environmental monitoring buoy. In general, the transfer velocity of environmental gases across the air-sea interface is obtained exclusively from empirical relationships with wind speeds. However, our monitoring data demonstrate that the agitation of the aqueous boundary layer is controlled significantly by tidal turbulence, similar to the control exercised by wind stress in the coastal ocean. The sea-to-air transfer of CH 4 is enhanced significantly during spring tide due to an increase in the gas transfer velocity and vertical CH 4 transport from bottom water to the surface layer. Thus, our unique time-series results imply that the sea-to-air transfer of gases, such as CH 4 , DMS, DMHg, N 2 O, CO 2 and 222 Rn, from highly enriched coastal bottom waters, is controlled not only by episodic wind events but also by regular tidal turbulence in the coastal ocean

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

Energy Technology Data Exchange (ETDEWEB)

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 both significant annual 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 methane in addition to other greenhouse gases (e.g. carbon dioxide) but the ultimate source of this methane flux has not been elucidated. Here we use dual stable isotope analysis (δ²H and δ¹³C) of CH₄(g) sampled from ten high-temperature geothermal pools in Yellowstone National Park to show that the predominant flux of CH4(g) is abiotic. The average δ¹³C and δ²H values of CH₄(g) emitted from hot springs (-26.7 (±2.4) and -236.9 (±12.0) ‰, respectively) are not consistent with biotic (microbial or thermogenic) methane sources, but are within previously reported ranges for abiotic methane production. Correlation between δ¹³C_CH4 and δ¹³C-dissolved inorganic C (DIC) also suggests that CO₂ is a parent C source for the observed CH₄(g). Moreover, CH₄-CO₂ isotopic geothermometry was used to estimate CH₄(g) formation temperatures ranging from ~ 250 - 350°C, which is just below the temperature estimated for the hydrothermal reservoir and consistent with the hypothesis that subsurface, rock-water interactions are responsible for large methane fluxes from this volcanic system. An understanding of conditions leading to the abiotic production of methane and associated isotopic signatures are central to understanding the evolutionary history of deep carbon sources on Earth.

Raman spectroscopic characterization of CH4 density over a wide range of temperature and pressure

Science.gov (United States)

Shang, Linbo; Chou, I-Ming; Burruss, Robert; Hu, Ruizhong; Bi, Xianwu

2014-01-01

The positions of the CH4 Raman ν1 symmetric stretching bands were measured in a wide range of temperature (from −180 °C to 350 °C) and density (up to 0.45 g/cm3) using high-pressure optical cell and fused silica capillary capsule. The results show that the Raman band shift is a function of both methane density and temperature; the band shifts to lower wavenumbers as the density increases and the temperature decreases. An equation representing the observed relationship among the CH4 ν1 band position, temperature, and density can be used to calculate the density in natural or synthetic CH4-bearing inclusions.

Ion irradiation of CH4-containing icy mixtures

International Nuclear Information System (INIS)

Baratta, G.A.; Domingo, M.; Ferini, G.; Leto, G.; Palumbo, M.E.; Satorre, M.A.; Strazzulla, G.

2003-01-01

We have studied by infrared absorption spectroscopy the effects of ion irradiation with 60 keV Ar 2+ ions on pure methane (CH 4 ) ice at 12 K and mixtures with water (H 2 O) and nitrogen (N 2 ). Ion irradiation, among other effects, causes the rupture of original molecular bonds and the formation of molecular species not present in the initial ice. Here we present the experimental results and discuss their astrophysical relevance

Quantifying the Variability of CH4 Emissions from Pan-Arctic Lakes with Lake Biogeochemical and Landscape Evolution Models

Science.gov (United States)

Tan, Z.; Zhuang, Q.

2014-12-01

Recent studies in the arctic and subarctic show that CH4 emissions from pan-arctic lakes are playing much more significant roles in the regional carbon cycling than previously estimated. Permafrost thawing due to pronounced warming at northern high latitudes affects lake morphology, changing its CH4 emissions. Thermokarst can enlarge the extent of artic lakes, exposing stable ancient carbon buried in the permafrost zone for degradation and changing a previously known carbon sink to a large carbon source. In some areas, the thawing of subarctic discontinuous and isolated permafrost can diminish thermokarst lakes. To date, few models have considered these important hydrological and biogeochemical processes to provide adequate estimation of CH4 emissions from these lakes. To fill this gap, we have developed a process-based climate-sensitive lake biogeochemical model and a landscape evolution model, which have been applied to quantify the state and variability of CH4 emissions from this freshwater system. Site-level experiments show the models are capable to capture the spatial and temporal variability of CH4 emissions from lakes across Siberia and Alaska. With the lake biogeochemical model solely, we estimate that the magnitude of CH4 emissions from lakes is 13.2 Tg yr-1 in the north of 60 ºN at present, which is on the same order of CH4 emissions from northern high-latitude wetlands. The maximum increment is 11.8 Tg CH4 yr-1 by the end of the 21st century when the worst warming scenario is assumed. We expect the landscape evolution model will improve the existing estimates.

Adsorption of CH4 on nitrogen- and boron-containing carbon models of coal predicted by density-functional theory

Science.gov (United States)

Liu, Xiao-Qiang; Xue, Ying; Tian, Zhi-Yue; Mo, Jing-Jing; Qiu, Nian-Xiang; Chu, Wei; Xie, He-Ping

2013-11-01

Graphene doped by nitrogen (N) and/or boron (B) is used to represent the surface models of coal with the structural heterogeneity. Through the density functional theory (DFT) calculations, the interactions between coalbed methane (CBM) and coal surfaces have been investigated. Several adsorption sites and orientations of methane (CH4) on graphenes were systematically considered. Our calculations predicted adsorption energies of CH4 on graphenes of up to -0.179 eV, with the strongest binding mode in which three hydrogen atoms of CH4 direct to graphene surface, observed for N-doped graphene, compared to the perfect (-0.154 eV), B-doped (-0.150 eV), and NB-doped graphenes (-0.170 eV). Doping N in graphene increases the adsorption energies of CH4, but slightly reduced binding is found when graphene is doped by B. Our results indicate that all of graphenes act as the role of a weak electron acceptor with respect to CH4. The interactions between CH4 and graphenes are the physical adsorption and slightly depend upon the adsorption sites on graphenes and the orientations of methane as well as the electronegativity of dopant atoms in graphene.

Modified ZIF-8 mixed matrix membrane for CO2/CH4 separation

Science.gov (United States)

Nordin, Nik Abdul Hadi Md; Ismail, Ahmad Fauzi; Misdan, Nurasyikin; Nazri, Noor Aina Mohd

2017-10-01

Tunability of metal-organic frameworks (MOFs) properties enables them to be tailored for specific applications. In this study, zeolitic imidazole framework 8 (ZIF-8), sub-class of MOF, underwent pre-synthesis and post-synthesis modifications. The pre-synthesis modification using GO (ZIF-8/GO) shows slight decrease in textural properties, while the post-synthesis modification using amine solution (ZIF-8/NH2) resulted in superior BET surface area and pore volume. Mixed matrix membranes (MMMs) derived from polysulfone (PSf) and the modified ZIF-8s were then prepared via dry/wet phase inversion. The polymer chain flexibility of the resulted MMMs shows rigidification, where ZIF-8/NH2 as filler resulting higher rigidification compared to ZIF-8/GO. The MMMs were further subjected to pure CO2 and CH4 gas permeation experiments. The PSf/ZIF-8/NH2 shows superior CO2/CH4 selectivity (88% increased) while sacrificing CO2 permeance due to combination of severe polymer chain rigidification and the presence of CO2-philic group, amine. Whereas, the PSf/ZIF-8/GO possess 64% increase in CO2 permeance without notable changes in CO2/CH4 selectivity.

Plant-mediated CH4 transport and C gas dynamics quantified in-situ in a Phalaris arundinacea-dominant wetland

DEFF Research Database (Denmark)

Jensen, Louise Askær; Elberling, Bo; Friborg, Thomas

2011-01-01

passive. Thus, diurnal variations are less important in contrast to wetland vascular plants facilitating convective gas flow. Despite of plant-dominant CH4 transport, net CH4 fluxes were low (–0.005–0.016 µmol m-2 s-1) and annually less than 1% of the annual C-CO2 assimilation. This is considered a result......±35% of ecosystem CH4 emissions were plant-mediated, but data show no evidence of significant diurnal variations related to convective gas flow regardless of season or plant growth stages. Therefore, despite a high percentage of arenchyma, P. arundinacea-mediated CH4 transport is interpreted to be predominantly...

Thermodynamic activity of saturated solutions of CsClO4 in ethylene glycol and its analogs of the HOCH2(CH2CH2O)nCH2OH series

International Nuclear Information System (INIS)

Krasnoperova, A.P.; Ivanova, E.F.; Kijko, S.M.; Yukhno, G.D.

1997-01-01

Solubility of CsClO 4 in ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with molar mass 300 and 400 in the temperature range of 273.15-318.15 K has been ascertained by the method of radioactive indicators. Dependence of saturated solutions activity on temperature, dielectric permittivity and the number of (CH 2 CH 2 O) ether groups in glycols is discussed

Flux and distribution of methane (CH4) in the Gunsan Basin of the southeastern Yellow Sea, off the Western Korea.

Science.gov (United States)

Lee, Jun-Ho; Woo, Han Jun; Son, Seung-Kyu; Kim, Moonkoo; Lee, Dong-Hun; Tsunogai, Urumu; Jeong, Kap-Sik

2018-04-16

The flux and distribution of methane (CH 4 ) was investigated in the seawater column at 14 stations in the Gunsan Basin, the southeastern part of Yellow Sea from 2013 to 2015. Here CH 4 is concentrated 2.4-4.7 (3.4 ± 0.7) nM in the surface and 2.5-7.4 (5.2 ± 1.7) nM in the bottom layer. The CH 4 saturation ratios ranged from 65.5% to 295.5% (162.6 ± 68.7), comprising the mean sea-to-air CH 4 flux of 3.8 to 25.3 (15.6 ± 5.5) µM m -2 d -1 . Methane concentration was largely different in the upper and the lower seawater layers that is separated by the thermocline of which depth is variable (20-60 m) depending on the time of sampling. The concentration of seawater dissolved CH 4 is high between the bottom surface of the thermocline layer and the sea floor. Generally it tends to decrease from the south-westernmost part of the basin toward the west coast of Korea. This distribution pattern of CH 4 seems to result from the CH 4 supply by decomposition of organic matters produced in the upper seawater layer that is superimposed by the larger supply from the underlying sediment layer especially beneath the thermocline. The latter is manifested by ubiquitous CH 4 seeps from the seafloor sediments.

In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

KAUST Repository

Al-Sabban, Bedour

2017-05-02

Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests

Selective Generation of the Radical Cation Isomers [CH3CN](•+) and [CH2CNH](•+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C2H4.

Science.gov (United States)

Polášek, Miroslav; Zins, Emilie-Laure; Alcaraz, Christian; Žabka, Ján; Křížová, Věra; Giacomozzi, Linda; Tosi, Paolo; Ascenzi, Daniela

2016-07-14

Experimental and theoretical studies have been carried out to demonstrate the selective generation of two different C2H3N(+) isomers, namely, the acetonitrile [CH3CN](•+) and the ketenimine [CH2CNH](•+) radical cations. Photoionization and dissociative photoionization experiments from different neutral precursors (acetonitrile and butanenitrile) have been performed using vacuum ultraviolet (VUV) synchrotron radiation in the 10-15 eV energy range, delivered by the DESIRS beamline at the SOLEIL storage ring. For butanenitrile (CH3CH2CH2CN) an experimental ionization threshold of 11.29 ± 0.05 eV is obtained, whereas the appearance energy for the formation of [CH2CNH](•+) fragments is 11.52 ± 0.05 eV. Experimental findings are fully supported by theoretical calculations at the G4 level of theory (ZPVE corrected energies at 0 K), giving a value of 11.33 eV for the adiabatic ionization energy of butanenitrile and an exothermicity of 0.49 for fragmentation into [CH2CNH](•+) plus C2H4, hampered by an energy barrier of 0.29 eV. The energy difference between [CH3CN](•+) and [CH2CNH](•+) is 2.28 eV (with the latter being the lowest energy isomer), and the isomerization barrier is 0.84 eV. Reactive monitoring experiments of the [CH3CN](•+) and [CH2CNH](•+) isomers with C2H4 have been performed using the CERISES guided ion beam tandem mass spectrometer and exploiting the selectivity of ethylene that gives exothermic charge exchange and proton transfer reactions with [CH3CN](•+) but not with [CH2CNH](•+) isomers. In addition, minor reactive channels are observed leading to the formation of new C-C bonds upon reaction of [CH3CN](•+) with C2H4, and their astrochemical implications are briefly discussed.

Correlations between substrate availability, dissolved CH₄, and CH₄ emissions in an arctic wetland subject to warming and plant removal

DEFF Research Database (Denmark)

Nielsen, Cecilie Skov; Michelsen, Anders; Strobel, Bjarne W.

2017-01-01

The Arctic is warming which may potentially affect substrate availability, organic matter decomposition, plant growth, and plant species composition. This may lead to changes in the exchange of methane (CH4) and carbon dioxide (CO2) between the soil system and the atmosphere. Yet the correlations...

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO_2(CH_3SO_3)_2, UO_2(CH_3SO_3)_2, ReO_3(CH_3SO_3), VO(CH_3SO_3)_2, and V_2O_3(CH_3SO_3)_4 and their thermal decomposition under N_2 and O_2 atmosphere

International Nuclear Information System (INIS)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S.

2011-01-01

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO_3, UO_2(CH_3COO)_2.2 H_2O, Re_2O_7(H_2O)_2, and V_2O_5 with CH_3SO_3H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO_2(CH_3SO_3)_2 (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm"3, Z=8) contains [MoO_2] moieties connected by [CH_3SO_3] ions to form layers parallel to (100). UO_2(CH_3SO_3)_2 (P2_1/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) "c"i"r"c"l"e, V=1.8937(3) nm"3, Z=8) consists of linear UO_2"2"+ ions coordinated by five [CH_3SO_3] ions, forming a layer structure. VO(CH_3SO_3)_2 (P2_1/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) "c"i"r"c"l"e, V=0.8290(2) nm"3, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO_3(CH_3SO_3) (P anti 1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2) "c"i"r"c"l"e, V=1.1523(4) nm"3, Z=8) a chain structure exhibiting infinite O-[ReO_2]-O-[ReO_2]-O chains is formed. Each [ReO_2]-O-[ReO_2] unit is coordinated by two bidentate [CH_3SO_3] ions. V_2O_3(CH_3SO_3)_4 (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm"3, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH_3SO_3] ligands. Additional methanesulfonate ions connect the [V_2O_3] groups along [001]. Thermal decomposition of the compounds was monitored under N_2 and O_2 atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N_2 the decomposition proceeds with reduction of the metal leading to the oxides MoO_2, U_3O_7, V_4O_7, and VO_2; for MoO_2(CH_3SO_3)_2, a small amount of MoS_2 is formed. If the thermal decomposition is carried out in a atmosphere of O_2 the oxides MoO_3 and V_2O_5 are formed. (Copyright copyright 2011 WILEY-VCH Verlag

Summary of LOX/CH4 Thruster Technology Development at NASA/MSFC

Science.gov (United States)

Greene, Sandra Elam

2015-01-01

In recent years, a variety of injectors for liquid oxygen (LOX) and methane (CH4) propellant systems have been designed, fabricated, and demonstrated with hot-fire testing at Marshall Space Flight Center (MSFC). Successful designs for liquid methane (LCH4) and gaseous methane (GCH4) have been developed. A variety of chambers, including a transpiration cooled design, along with uncooled ablatives and refractory metals, have also been hot-fire tested by MSFC for use with LOX/LCH4 injectors. Hot-fire testing has also demonstrated multiple ignition source options. Heat flux data for selected injectors has been gathered by testing with a calorimeter chamber. High performance and stable combustion have been demonstrated, along with designs for thrust levels ranging from 500 to 7,000 lbf. The newest LOX/CH4 injector and chamber developed by MSFC have been fabricated with additive manufacturing techniques and include unique design features to investigate regenerative cooling with methane. This low cost and versatile hardware offers a design for 4,000 lbf thrust and will be hot-fire tested at MSFC in 2015. Its design and operation can easily be scaled for use in systems with thrust levels up to 25,000 lbf.

Variable temperature ion trap studies of CH4+ + H2, HD and D2: negative temperature dependence and significant isotope effect

International Nuclear Information System (INIS)

Asvany, O.; Savic, I.; Schlemmer, S.; Gerlich, D.

2004-01-01

Reactions of methane cations, CH 4 + , with H 2 , HD and D 2 have been studied in a variable temperature 22-pole ion trap from room temperature down to 15 K. The formation of CH 5 + in collisions with H 2 is slow at 300 K, but it becomes faster by at least one order of magnitude when the temperature is lowered to 15 K. This behavior is tentatively explained with a longer complex lifetime at low temperatures. However, since tunneling is most probably not responsible for product formation, other dynamical or statistical restrictions must be responsible for the negative temperature dependence. In collisions of CH 4 + with HD, the CH 5 + product ion (68% at 15 K) prevails over CH 4 D + (32%). Reaction of CH 4 + with D 2 is found to be much slower than with H 2 or HD. The rate coefficient for converting CH 4 + into CH 3 D + by H-D exchange has been determined to be smaller than 10 -12 cm 3 /s, indicating that scrambling in the CH 6 + complex is very unlikely

CH4 and N2O from mechanically turned windrow and vermicomposting systems following in-vessel pre-treatment

International Nuclear Information System (INIS)

Hobson, A.M.; Frederickson, J.; Dise, N.B.

2005-01-01

Methane (CH 4 ) and nitrous oxide (N 2 O) are included in the six greenhouse gases listed in the Kyoto protocol that require emission reduction. To meet reduced emission targets, governments need to first quantify their contribution to global warming. Composting has been identified as an important source of CH 4 and N 2 O. With increasing divergence of biodegradable waste from landfill into the composting sector, it is important to quantify emissions of CH 4 and N 2 O from all forms of composting and from all stages. This study focuses on the final phase of a two stage composting process and compares the generation and emission of CH 4 and N 2 O associated with two differing composting methods: mechanically turned windrow and vermicomposting. The first stage was in-vessel pre-treatment. Source-segregated household waste was first pre-composted for seven days using an in-vessel system. The second stage of composting involved forming half of the pre-composted material into a windrow and applying half to vermicomposting beds. The duration of this stage was 85 days and CH 4 and N 2 O emissions were monitored throughout for both systems. Waste samples were regularly subjected to respirometry analysis and both processes were found to be equally effective at stabilising the organic matter content. The mechanically turned windrow system was characterised by emissions of CH 4 and to a much lesser extent N 2 O. However, the vermicomposting system emitted significant fluxes of N 2 O and only trace amounts of CH 4 . In-vessel pre-treatment removed considerable amounts of available C and N prior to the second stage of composting. This had the effect of reducing emissions of CH 4 and N 2 O from the second stage compared to emissions from fresh waste found in other studies. The characteristics of each of the two composting processes are discussed in detail. Very different mechanisms for emission of CH 4 and N 2 O are proposed for each system. For the windrow system, development

Efficient Synthesis of Ethanol from CH4 and Syngas on a Cu-Co/TiO2 Catalyst Using a Stepwise Reactor

Science.gov (United States)

Zuo, Zhi-Jun; Peng, Fen; Huang, Wei

2016-10-01

Ethanol synthesis from CH4 and syngas on a Cu-Co/TiO2 catalyst is studied using experiments, density functional theory (DFT) and microkinetic modelling. The experimental results indicate that the active sites of ethanol synthesis from CH4 and syngas are Cu and CoO, over which the ethanol selectivity is approximately 98.30% in a continuous stepwise reactor. DFT and microkinetic modelling results show that *CH3 is the most abundant species and can be formed from *CH4 dehydrogenation or through the process of *CO hydrogenation. Next, the insertion of *CO into *CH3 forms *CH3CO. Finally, ethanol is formed through *CH3CO and *CH3COH hydrogenation. According to our results, small particles of metallic Cu and CoO as well as a strongly synergistic effect between metallic Cu and CoO are beneficial for ethanol synthesis from CH4 and syngas on a Cu-Co/TiO2 catalyst.

Edge effects on N2O, NO and CH4 fluxes in two temperate forests.

Science.gov (United States)

Remy, Elyn; Gasche, Rainer; Kiese, Ralf; Wuyts, Karen; Verheyen, Kris; Boeckx, Pascal

2017-01-01

Forest ecosystems may act as sinks or sources of nitrogen (N) and carbon (C) compounds, such as the climate relevant trace gases nitrous oxide (N 2 O), nitric oxide (NO) and methane (CH 4 ). Forest edges, which catch more atmospheric deposition, have become important features in European landscapes and elsewhere. Here, we implemented a fully automated measuring system, comprising static and dynamic measuring chambers determining N 2 O, NO and CH 4 fluxes along an edge-to-interior transect in an oak (Q. robur) and a pine (P. nigra) forest in northern Belgium. Each forest was monitored during a 2-week measurement campaign with continuous measurements every 2h. NO emissions were 9-fold higher than N 2 O emissions. The fluxes of NO and CH 4 differed between forest edge and interior, but not for N 2 O. This edge effect was more pronounced in the oak than in the pine forest. In the oak forest, edges emitted less NO (on average 60%) and took up more CH 4 (on average 177%). This suggests that landscape structure can play a role in the atmospheric budgets of these climate relevant trace gases. Soil moisture variation between forest edge and interior was a key variable explaining the magnitude of NO and CH 4 fluxes in our measurement campaign. To better understand the environmental impact of N and C trace gas fluxes from forest edges, additional and long-term measurements in other forest edges are required. Copyright © 2016 Elsevier B.V. All rights reserved.

Measurements and Interpretation of Surface Mixing Ratios of CH4 and CO and δ 13C and δ D of CH4 in Air from Pacific Ocean Transects Between Auckland, New Zealand and Los Angeles, California

Science.gov (United States)

Ajie, H. O.; Tyler, S. C.; Gotoh, A. A.; McMillan, A. M.; Rice, A. L.; Lowe, D. C.

2003-12-01

We report on measurements of atmospheric CH4 and CO mixing ratios and δ 13C of CH4 from air samples collected every 2.5 to 5° latitude along a transect over the Pacific Ocean using container ships of P&O Nedlloyd (formerly Blue Star) shipping line. Data presented here begins in June 1996 and extends to January 2002. Scientists from the National Institute of Water and Atmospheric Research in New Zealand and from University of California, Irvine alternate sampling trips so that a transect between Auckland, New Zealand (35° S) and Los Angeles, California (35° N) can be sampled over a period of ˜15 days approximately every four months. Data sets from the two laboratories are intercalibrated through a sample exchange program. The data provide detail on the spatial and seasonal variation of CH4 and CO mixing ratios and stable isotope ratios of CH4 over the Pacific equatorial region, including the Intertropical Convergence Zone (ITCZ) and both northern and southern temperate zones to about 30° latitude, including the South Pacific Convergence Zone (SPCZ). Data from 18 transect samplings so far clearly show that δ 13C in the mid latitudes of both hemispheres are ˜6 months out of phase. In June, a minimum in δ 13C CH4 in the southern hemisphere (SH) coincides approximately with the maximum in the northern hemisphere (NH) seasonal cycle. Because the NH is less enriched in 13C than the SH this situation results in a remarkably flat gradient between 30° N and 30° S. In November the opposite situation occurs with the SH mid latitude maximum coinciding with the minimum in the NH cycle, leading to a relatively large gradient of ˜0.5‰ between the hemispheres. We discuss how CH4 and CO mixing ratios are related to the changing positions and strengths of the ITCZ and SPCZ and how this data can be used in multi-dimensional models of atmospheric chemistry and transport to better define CH4 sources and sinks both temporally and spatially.

Effects of coastal marsh conversion to shrimp aquaculture ponds on CH4 and N2O emissions

Science.gov (United States)

Yang, P.; Bastviken, D.; Lai, D. Y. F.; Jin, B. S.; Mou, X. J.; Tong, C.; Yao, Y. C.

2017-12-01

In this study, we compared the CH4 and N2O fluxes from a tidal brackish Cyperus malaccensis marsh ecosystem and nearby shrimp ponds, converted from C. malaccensis marsh in the last 3-4 years, in the Min River estuary of southeast China over the aquaculture period of the year. Significant differences in CH4 and N2O fluxes were observed in space (between brackish marsh and shrimp ponds) and in time (between sampling occasions that were distributed over the aquaculture period). CH4 fluxes from the shrimp ponds were on an average 10-fold higher than from the brackish marsh. N2O emissions, on the other hand, were lower from the shrimp pond (25% of the emissions from the brackish marsh). Accessory data indicates that these patterns were primarily linked to water level variability and temperature (all fluxes), sediment porewater sulfate concentrations (CH4 flux) and total nitrogen concentrations (N2O flux). Our research demonstrates that the coastal marsh ecosystem converted to aquaculture ponds considerably alter emissions of CH4 and N2O and provides input to the global discussion on how to account for emissions from various types of flooded land in greenhouse gas inventories.

Are CH2O measurements in the marine boundary layer suitable for testing the current understanding of CH4 photooxidation?: A model study

Science.gov (United States)

Wagner, V.; von Glasow, R.; Fischer, H.; Crutzen, P. J.

2002-02-01

On the basis of a data set collected during the Indian Ocean Experiment (INDOEX) campaign 1999, we investigated the formaldehyde (CH2O) budget in the southern Indian Ocean (SIO). With a photochemical box model we simulated the contribution of methane and nonmethane volatile organic compounds to the CH2O budget. To identify the reactions and model constraints that introduce the largest uncertainties in the modeled CH2O concentration, we carried out a local sensitivity analysis. Furthermore, a Monte Carlo method was used to assess the global error of the model predictions. According to this analysis the 2σ uncertainty in the modeled CH2O concentration is 49%. The deviation between observed (200 +/- 70 parts per trillion by volume (pptv) (2σ)) and modeled (224 +/- 110 pptv (2σ)) daily mean CH2O concentration is 12%. However, the combined errors of model and measurement are such that deviations as large as 65% are not significant at the 2σ level. Beyond the ``standard'' photochemistry we analyzed the impact of halogen and aerosol chemistry on the CH2O concentration and investigated the vertical distribution of CH2O in the marine boundary layer (MBL). Calculations with the Model of Chemistry Considering Aerosols indicate that, based on the current understanding, halogen chemistry and aerosol chemistry have no significant impact on the CH2O concentration under conditions encountered in the SIO. However, a detailed investigation including meteorological effects such as precipitation scavenging and convection reveals an uncertainty in state-of-the-art model predictions for CH2O in the MBL that is too large for a meaningful test of the current understanding of CH4 photooxidation.

Reducing CH{sub 4} and CO{sub 2} emissions from waterlogged paddy soil with biochar

Energy Technology Data Exchange (ETDEWEB)

Liu, Yuxue; Yang, Min; Chen, Yingxu; Wu, Weixiang [Zhejiang Univ., Hangzhou (China). Inst. of Environmental Science and Technology; Wu, Yimin [Hangzhou No. 2 High School, Hangzhou (China); Wang, Hailong [Scion, Rotorua (New Zealand)

2011-09-15

Purpose: A potential means to diminish increasing levels of CO{sub 2} in the atmosphere is the use of pyrolysis to convert biomass into biochar, which stabilizes the carbon (C) that is then applied to soil. Before biochar can be used on a large scale, especially in agricultural soils, its effects on the soil system need to be assessed. This is especially important in rice paddy soils that release large amounts of greenhouse gases to the atmosphere. Materials and methods: In this study, the effects of biochar on CH{sub 4} and CO{sub 2} emissions from paddy soil with and without rice straw added as an additional C source were investigated. The biochars tested were prepared from bamboo chips or rice straw which yielded bamboo char (BC) and straw char (SC), respectively. BC and SC were applied to paddy soil to achieve low, medium, and high rates, based on C contents of the biochars. The biochar-amended soils were incubated under waterlogged conditions in the laboratory. Results and discussion: Adding rice straw significantly increased CH{sub 4} and CO{sub 2} emissions from the paddy soil. However, when soils were amended with biochar, CH{sub 4} emissions were reduced. CH{sub 4} emissions from the paddy soil amended with BC and SC at high rate were reduced by 51.1% and 91.2%, respectively, compared with those without biochar. Methanogenic activity in the paddy soil decreased with increasing rates of biochar, whereas no differences in denaturing gradient gel electrophoresis patterns were observed. CO{sub 2} emission from the waterlogged paddy soil was also reduced in the biochar treatments. Conclusions: Our results showed that SC was more effective than BC in reducing CH{sub 4} and CO{sub 2} emissions from paddy soils. The reduction of CH{sub 4} emissions from paddy soil with biochar amendment may result from the inhibition of methanogenic activity or a stimulation of methylotrophic activity during the incubation period. (orig.)

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

Science.gov (United States)

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

Gully hotspot contribution to landscape methane (CH4) and carbon dioxide (CO2) fluxes in a northern peatland

International Nuclear Information System (INIS)

McNamara, N.P.; Plant, T.; Oakley, S.; Ward, S.; Wood, C.; Ostle, N.

2008-01-01

Peatlands are long term carbon catchments that sink atmospheric carbon dioxide (CO 2 ) and source methane (CH 4 ). In the uplands of the United Kingdom ombrotrophic blanket peatlands commonly exist within Calluna vulgaris (L.) dominated moorland ecosystems. These landscapes contain a range of topographical features that influence local hydrology, climate and plant community composition. In this study we examined the variation in ecosystem CO 2 respiration and net CH 4 fluxes from typical plant-soil systems in dendritic drainage gullies and adjacent blanket peat during the growing season. Typically, Eriophorum spp., Sphagnum spp. and mixed grasses occupied gullies while C. vulgaris dominated in adjacent blanket peat. Gross CO 2 respiration was highest in the areas of Eriophorum spp. (650 ± 140 mg CO 2 m -2 h -1 ) compared to those with Sphagnum spp. (338 ± 49 mg CO 2 m -2 h -1 ), mixed grasses (342 ± 91 mg CO 2 m -2 h -1 ) and C. vulgaris (174 ± 63 mg CO 2 m -2 h -1 ). Measurements of the net CH 4 flux showed higher fluxes from the Eriophorum spp (2.2 ± 0.6 mg CH 4 m -2 h -1 ) locations compared to the Sphagnum spp. (0.6 ± 0.4 mg CH 4 m -2 h -1 ), mixed grasses (0.1 ±0.1 mg CH 4 m -2 h -1 ) and a negligible flux detected from C. vulgaris (0.0 ± 0.0 mg CH 4 m -2 h -1 ) locations. A GIS approach was applied to calculate the contribution of gullies to landscape scale greenhouse gas fluxes. Findings from the Moor House National Nature Reserve in the UK showed that although gullies occupied only 9.3% of the total land surface, gullies accounted for 95.8% and 21.6% of the peatland net CH 4 and CO 2 respiratory fluxes, respectively. The implication of these findings is that the relative contribution of characteristic gully systems need to be considered in estimates of landscape scale peatland greenhouse gas fluxes

CH-TRU Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2005-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-10-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The reaction of fluorine atoms with methanol: yield of CH3O/CH2OH and rate constant of the reactions CH3O + CH3O and CH3O + HO2.

Science.gov (United States)

Assaf, Emmanuel; Schoemaecker, Coralie; Vereecken, Luc; Fittschen, Christa

2018-04-25

Xenondifluoride, XeF2, has been photolysed in the presence of methanol, CH3OH. Two reaction pathways are possible: F + CH3OH → CH2OH + HF and F + CH3OH → CH3O + HF. Both products, CH2OH and CH3O, will be converted to HO2 in the presence of O2. The rate constants for the reaction of both radicals with O2 differ by more than 3 orders of magnitude, which allows an unequivocal distinction between the two reactions when measuring HO2 concentrations in the presence of different O2 concentrations. The following yields have then been determined from time-resolved HO2 profiles: φCH2OH = (0.497 ± 0.013) and φCH3O = (0.503 ± 0.013). Experiments under low O2 concentrations lead to reaction mixtures containing nearly equal amounts of HO2 (converted from the first reaction) and CH3O (from the second reaction). The subsequent HO2 decays are very sensitive to the rate constants of the reaction between these two radicals and the following rate constants have been obtained: k(CH3O + CH3O) = (7.0 ± 1.4) × 10-11 cm3 s-1 and k(CH3O + HO2) = (1.1 ± 0.2) × 10-10 cm3 s-1. The latter reaction has also been theoretically investigated on the CCSD(T)//M06-2X/aug-cc-pVTZ level of theory and CH3OH + O2 have been identified as the main products. Using μVTST, a virtually pressure independent rate constant of k(CH3O + HO2) = 4.7 × 10-11 cm3 s-1 has been obtained, in good agreement with the experiment.

生物炭对土壤N2O和CH4排放影响的研究进展%Advances in Effects of Biochar on the Soil N2O and CH4 Emissions

Institute of Scientific and Technical Information of China (English)

颜永毫; 王丹丹; 郑纪勇

2013-01-01

In order to study the pathway and mechanism of biochar affecting soil N2O and CH4 emissions, based on comprehensive evaluation of published researches, the factors, pathway and mechanism that biochar affected soil N2O and CH4 emissions were analyzed, the principles of biochar addition in different types of soil were then proposed. The key problems that should be paid attention to in future studies were pointed out: (1) the characters of these two GHG emissions in soil should be explicited, the biochar type should be chosen according to the local soil conditions. (2) The time and amount of biochar addition should be reasonable. (3) Nowadays because of the differences of biochars and soil types that different scholars used, the research conclusions about the effects of biochar on the soil N2O and CH4 emissions were still controversial. In future, the more clear conclusions about the effects of biochar on the soil N2O and CH4 would be attained till the experiments of returning biochar into field according to the local soil type should be continued after the complement of biochar applying standard.%为了探讨生物炭对土壤N2O和CH4排放影响的途径和机理,在综合评述前人研究的基础上,就生物炭对土壤N2O和CH4排放的影响因素、途径和影响机理进行了分析,提出了不同土壤的生物炭施用原则,并指出了今后生物炭研究应注意的问题:(1)明确土壤中2种温室气体排放特点,园地制宜地选择合适的生物炭类型；(2)注意生物炭的添加时机和用量；(3)目前学者所用的生物炭类型以及土壤种类不同,关于生物炭影响土壤N2O和CH4排放的研究结论不同.在这方面的研究工作还应在完善生物炭施用标准的基础上,继续进行生物炭还田的本地化试验验证,才能为生物炭对土壤N2O和CH4排放的影响得出更明确的结论.

Calibration and field testing of cavity ring-down laser spectrometers measuring CH4, CO2, and δ13CH4 deployed on towers in the Marcellus Shale region

Directory of Open Access Journals (Sweden)

N. L. Miles

2018-03-01

Full Text Available Four in situ cavity ring-down spectrometers (G2132-i, Picarro, Inc. measuring methane dry mole fraction (CH4, carbon dioxide dry mole fraction (CO2, and the isotopic ratio of methane (δ13CH4 were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. In this paper, we describe laboratory and field calibration of the analyzers for tower-based applications and characterize their performance in the field for the period January–December 2016. Prior to deployment, each analyzer was tested using bottles with various isotopic ratios, from biogenic to thermogenic source values, which were diluted to varying degrees in zero air, and an initial calibration was performed. Furthermore, at each tower location, three field tanks were employed, from ambient to high mole fractions, with various isotopic ratios. Two of these tanks were used to adjust the calibration of the analyzers on a daily basis. We also corrected for the cross-interference from ethane on the isotopic ratio of methane. Using an independent field tank for evaluation, the standard deviation of 4 h means of the isotopic ratio of methane difference from the known value was found to be 0.26 ‰ δ13CH4. Following improvements in the field tank testing scheme, the standard deviation of 4 h means was 0.11 ‰, well within the target compatibility of 0.2 ‰. Round-robin style testing using tanks with near-ambient isotopic ratios indicated mean errors of −0.14 to 0.03 ‰ for each of the analyzers. Flask to in situ comparisons showed mean differences over the year of 0.02 and 0.08 ‰, for the east and south towers, respectively. Regional sources in this region were difficult to differentiate from strong perturbations in the background. During the afternoon hours, the median differences of the isotopic ratio measured at three of the towers, compared to the background tower, were &minus0.15 to 0.12 ‰ with standard deviations of the 10�

Calibration and field testing of cavity ring-down laser spectrometers measuring CH4, CO2, and δ13CH4 deployed on towers in the Marcellus Shale region

Science.gov (United States)

Miles, Natasha L.; Martins, Douglas K.; Richardson, Scott J.; Rella, Christopher W.; Arata, Caleb; Lauvaux, Thomas; Davis, Kenneth J.; Barkley, Zachary R.; McKain, Kathryn; Sweeney, Colm

2018-03-01

Four in situ cavity ring-down spectrometers (G2132-i, Picarro, Inc.) measuring methane dry mole fraction (CH4), carbon dioxide dry mole fraction (CO2), and the isotopic ratio of methane (δ13CH4) were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. In this paper, we describe laboratory and field calibration of the analyzers for tower-based applications and characterize their performance in the field for the period January-December 2016. Prior to deployment, each analyzer was tested using bottles with various isotopic ratios, from biogenic to thermogenic source values, which were diluted to varying degrees in zero air, and an initial calibration was performed. Furthermore, at each tower location, three field tanks were employed, from ambient to high mole fractions, with various isotopic ratios. Two of these tanks were used to adjust the calibration of the analyzers on a daily basis. We also corrected for the cross-interference from ethane on the isotopic ratio of methane. Using an independent field tank for evaluation, the standard deviation of 4 h means of the isotopic ratio of methane difference from the known value was found to be 0.26 ‰ δ13CH4. Following improvements in the field tank testing scheme, the standard deviation of 4 h means was 0.11 ‰, well within the target compatibility of 0.2 ‰. Round-robin style testing using tanks with near-ambient isotopic ratios indicated mean errors of -0.14 to 0.03 ‰ for each of the analyzers. Flask to in situ comparisons showed mean differences over the year of 0.02 and 0.08 ‰, for the east and south towers, respectively. Regional sources in this region were difficult to differentiate from strong perturbations in the background. During the afternoon hours, the median differences of the isotopic ratio measured at three of the towers, compared to the background tower, were &minus0.15 to 0.12 ‰ with standard deviations of the 10 min isotopic ratio differences of 0.8 �

Biodiversity effects of benthic ecosystem engineers on the spatial patterns of sediment CH4 concentration in an urban Neotropical coastal lagoon

Directory of Open Access Journals (Sweden)

Adriano Caliman

Full Text Available AIM: Biodiversity of sediment bioturbators has been shown to be important for to the magnitude and stability of benthic-pelagic processes. However, no study to date has evaluated the importance of the biodiversity of benthic invertebrate bioturbators to the spatial patterns of sediment CH4 concentration ([CH4]. Here we conducted a laboratorial experiment to test the following predictions: (1 Bioturbator species richness will reduce the sediment [CH4]; (2 individual bioturbator species (i.e. species composition will have different effects on sediment [CH4]; (3 and both the effects of bioturbator species richness and composition on sediment [CH4] will be dependent on sediment depth. METHODS: We manipulated the number and composition of three functional divergent benthic invertebrate bioturbators species that are widespread in South Atlantic coastal lagoons, in laboratorial sediment chambers containing the sediment and water of an urban impacted coastal lagoon RESULTS: Bioturbator species richness had no overall significant effect on sediment [CH4] when comparisons of sediment [CH4] were made among species richness levels. However, bioturbator species richness significantly reduced sediment [CH4] when species richness levels were compared to the control (defaunated treatments, but this effect was significant only at the deepest sediment layer. Furthermore, bioturbator species composition had significant, but distinct effects on the patterns of reduction in sediment [CH4], depending on the sediment depth and the bioturbator species. CONCLUSIONS: We conclude that both the number and composition of bioturbator species are important to determine the effects of benthic bioturbators on spatial patterns of sediment [CH4], but the strength of these effects depend on species traits that determine interspecific interactions strength across the sediment vertical niche space.

Implications for carbon processing beneath the Greenland Ice Sheet from dissolved CO2 and CH4 concentrations of subglacial discharge

Science.gov (United States)

Pain, A.; Martin, J.; Martin, E. E.

2017-12-01

Subglacial carbon processes are of increasing interest as warming induces ice melting and increases fluxes of glacial meltwater into proglacial rivers and the coastal ocean. Meltwater may serve as an atmospheric source or sink of carbon dioxide (CO2) or methane (CH4), depending on the magnitudes of subglacial organic carbon (OC) remineralization, which produces CO2 and CH4, and mineral weathering reactions, which consume CO2 but not CH4. We report wide variability in dissolved CO2 and CH4 concentrations at the beginning of the melt season (May-June 2017) between three sites draining land-terminating glaciers of the Greenland Ice Sheet. Two sites, located along the Watson River in western Greenland, drain the Isunnguata and Russell Glaciers and contained 1060 and 400 ppm CO2, respectively. In-situ CO2 flux measurements indicated that the Isunnguata was a source of atmospheric CO2, while the Russell was a sink. Both sites had elevated CH4 concentrations, at 325 and 25 ppm CH4, respectively, suggesting active anaerobic OC remineralization beneath the ice sheet. Dissolved CO2 and CH4 reached atmospheric equilibrium within 2.6 and 8.6 km downstream of Isunnguata and Russell discharge sites, respectively. These changes reflect rapid gas exchange with the atmosphere and/or CO2 consumption via instream mineral weathering. The third site, draining the Kiagtut Sermiat in southern Greenland, had about half atmospheric CO2 concentrations (250 ppm), but approximately atmospheric CH4 concentrations (2.1 ppm). Downstream CO2 flux measurements indicated ingassing of CO2 over the entire 10-km length of the proglacial river. CO2 undersaturation may be due to more readily weathered lithologies underlying the Kiagtut Sermiat compared to Watson River sites, but low CH4 concentrations also suggest limited contributions of CO2 and CH4 from OC remineralization. These results suggest that carbon processing beneath the Greenland Ice Sheet may be more variable than previously recognized

Pure- and mixed-gas CO2/CH4 separation properties of PIM-1 and an amidoxime-functionalized PIM-1

KAUST Repository

Swaidan, Raja

2014-05-01

The prototypical solution-processable polymer of intrinsic microporosity, PIM-1, and derivatives thereof offer combinations of permeability and selectivity that make them potential candidate materials for membrane-based gas separations. Paramount to the design and evaluation of PIMs for economical natural gas sweetening is a high and stable CO2/CH4 selectivity under realistic, mixed-gas conditions. Here, amidoxime-functionalized PIM-1 (AO-PIM-1) was prepared and examined for fundamental structure/property relationships. Qualitative NLDFT pore-size distribution analyses of physisorption isotherms (N2 at -196 oC; CO2 at 0 oC) reveal a tightened microstructure indicating size-sieving ultra-microporosity (<7Å). AO-PIM-1 demonstrated a three-fold increase in αD(CO2/CH4) over PIM-1, surpassing the 2008 upper bound with P(CO2)=1153Barrer and ideal α(CO2/CH4)=34. Under a 50:50 CO2:CH4 mixed-gas feed, AO-PIM-1 showed less selectivity loss than PIM-1, maintaining a mixed-gas α(CO2/CH4) ~21 across a 20bar pressure range. Conversely, PIM-1 endured up to 60% increases in mixed-gas CH4 permeability over pure-gas values concurrent with a selectivity of only ~8 at 20bar. A pervasive intermolecular hydrogen bonding network in AO-PIM-1 predominantly yields a rigidified microstructure that mitigates CO2-induced matrix dilations, reducing detrimental mixed-gas CH4 copermeation. © 2014 Elsevier B.V.

CMS (Carbon Monitoring System) Methane (CH4) Flux for North America 0.5 degree x 0.667 degree V1 (CMS_CH4_FLX_NA) at GES DISC

Data.gov (United States)

National Aeronautics and Space Administration — The CMS Methane (CH4) Flux for North America data set contains estimates of methane emission in North America based on an inversion of the GEOS-Chem chemical...

Direct Measurements of Leaf Level CH4 and CO2 Exchange in a Boreal Forest

Science.gov (United States)

Crill, P.; Lindroth, A.; Vestin, P.; Båth, A.

2008-12-01

Reports of aerobic CH4 sources from leaves and litter of a variety of forests and plant functional types have added a potential mystery to our understanding of CH4 dynamics especially if these sources contribute enough to have a significant impact on the global budget. We have made direct measurements of leaf level CH4 and CO2 exchange using a quartz branch cuvette in a boreal forest in Norunda, Sweden since August of this year. The cuvette was temperature controlled and was designed to close for 5 minutes every 30 minutes. Air was circulated to a Los Gatos CH4/CO2 infrared absorption laser spectrometer. Air and cuvette temperatures, PAR and UV radiation (Kipp and Zonen, CUV4; spectral range 300-380 nm) were measured at the branch chamber. The study was made in the Norunda 100 years old stand consisting of a mixture of Scots pine (Pinus sylvestris L.) , Birch (Betula sp.) and Norway spruce (Picea abies (L.) Karst.). The cuvette was moved between trees at roughly 5 day intervals. A null empty cuvette period was included in the rotation. The initial data show the expected CO2 uptake correlated with incident PAR and low rates of emission at night. However, there was no clear pattern of emissions detectable in the CH4. We estimate that we should be able to resolve a change of 0.5 ppbv CH4 min- 1 with our analytical setup. Both the daytime (1000-1600) and nighttime (2200-0400) averages were less than our detection. Even on very sunny days with high PAR and UV flux values, no consistent pattern was detectable. The lack of a distinct signal may be due to the fact that the past month has been very rainy, it is late in the growth season at these latitudes and sun angles are increasing quickly. The trees were at the northern edge of a clearing and we were also measuring mid height (2-3 m) leaves and branches of young trees. The branch cuvette design can also be optimized to improve its sensitivity.

Flask sample measurements for CO2, CH4 and CO using cavity ring-down spectrometry

Science.gov (United States)

Wang, J.-L.; Jacobson, G.; Rella, C. W.; Chang, C.-Y.; Liu, I.; Liu, W.-T.; Chew, C.; Ou-Yang, C.-F.; Liao, W.-C.; Chang, C.-C.

2013-08-01

In recent years, cavity ring-down spectrometry (CRDS) has been demonstrated to be a highly sensitive, stable and fast analytical technique for real-time in situ measurements of greenhouse gases. In this study, we propose the technique (which we call flask-CRDS) of analyzing whole air flask samples for CO2, CH4 and CO using a custom gas manifold designed to connect to a CRDS analyzer. Extremely stable measurements of these gases can be achieved over a large pressure range in the flask, from 175 to 760 Torr. The wide pressure range is conducive to flask sample measurement in three ways: (1) flask samples can be collected in low-pressure environments (e.g. high-altitude locations); (2) flask samples can be first analyzed for other trace gases with the remaining low-pressure sample for CRDS analysis of CO2, CH4 and CO; and (3) flask samples can be archived and re-analyzed for validation. The repeatability of this method (1σ of 0.07 ppm for CO2, 0.4 ppb for CH4, and 0.5 ppb for CO) was assessed by analyzing five canisters filled with the same air sample to a pressure of 200 Torr. An inter-comparison of the flask-CRDS data with in-situ CRDS measurements at a high-altitude mountain baseline station revealed excellent agreement, with differences of 0.10 ± 0.09 ppm (1σ) for CO2 and 0.9 ± 1.0 ppb for CH4. This study demonstrated that the flask-CRDS method was not only simple to build and operate but could also perform highly accurate and precise measurements of atmospheric CO2, CH4 and CO in flask samples.

CH-53K Heavy Lift Replacement Helicopter (CH-53K)

Science.gov (United States)

2015-12-01

Selected Acquisition Report (SAR) RCS: DD-A&T(Q&A)823-390 CH-53K Heavy Lift Replacement Helicopter (CH-53K) As of FY 2017 President’s Budget...December 2015 SAR March 4, 2016 10:04:18 UNCLASSIFIED 4 Col Henry Vanderborght PMA-261 Heavy Lift Helicopters Program Executive Office - Air, Anti...757-5780 Fax: 301-757-5109 DSN Phone: 757-5780 DSN Fax: 757-5109 Date Assigned: May 29, 2014 Program Information Program Name CH-53K Heavy Lift

A theoretical study of CH4 dissociation on pure and gold-alloyed Ni(111) surfaces

DEFF Research Database (Denmark)

Kratzer, P.; Hammer, Bjørk; Nørskov, Jens Kehlet

1996-01-01

We present a density functional theory study of the first step of CH4 adsorption on the Ni(111) surface, dissociation into adsorbed CH3 and H. The rupture of the C-H bond occurs preferentially on top of a Ni atom, with a dissociation barrier of about 100 kJ/mol (including zero point corrections......). The transition state involves considerable internal excitation of the molecule. The active C-H bond is both stretched to 1.6 Angstrom and tilted relative to the methyl group. A normal mode analysis shows that the reaction coordinate is mainly a C-H stretch, while the orientation of the C-H bond relative...... to the surface is responsible for the highest real mode. Alloying the surface with gold also affects the reactivity of the Ni atoms on adjacent surface sites. The dissociation barrier is increased by 16 and 38 kJ/mol for a Ni atom with one or two gold neighbors, respectively. We attribute these changes...

Adsorption of CH{sub 4} on nitrogen- and boron-containing carbon models of coal predicted by density-functional theory

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiao-Qiang [College of Chemistry, Key Lab of Green Chemistry and Technology in Ministry of Education, Sichuan University, Chengdu 610064 (China); Xue, Ying, E-mail: yxue@scu.edu.cn [College of Chemistry, Key Lab of Green Chemistry and Technology in Ministry of Education, Sichuan University, Chengdu 610064 (China); Tian, Zhi-Yue; Mo, Jing-Jing; Qiu, Nian-Xiang [College of Chemistry, Key Lab of Green Chemistry and Technology in Ministry of Education, Sichuan University, Chengdu 610064 (China); Chu, Wei [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Xie, He-Ping [Key Laboratory of Energy Engineering Safety and Mechanics on Disasters, The Ministry of Education, Sichuan University, Chengdu 610065 (China)

2013-11-15

Graphene doped by nitrogen (N) and/or boron (B) is used to represent the surface models of coal with the structural heterogeneity. Through the density functional theory (DFT) calculations, the interactions between coalbed methane (CBM) and coal surfaces have been investigated. Several adsorption sites and orientations of methane (CH{sub 4}) on graphenes were systematically considered. Our calculations predicted adsorption energies of CH{sub 4} on graphenes of up to −0.179 eV, with the strongest binding mode in which three hydrogen atoms of CH{sub 4} direct to graphene surface, observed for N-doped graphene, compared to the perfect (−0.154 eV), B-doped (−0.150 eV), and NB-doped graphenes (−0.170 eV). Doping N in graphene increases the adsorption energies of CH{sub 4}, but slightly reduced binding is found when graphene is doped by B. Our results indicate that all of graphenes act as the role of a weak electron acceptor with respect to CH{sub 4}. The interactions between CH{sub 4} and graphenes are the physical adsorption and slightly depend upon the adsorption sites on graphenes and the orientations of methane as well as the electronegativity of dopant atoms in graphene.

Climate change impact of livestock CH4 emission in India: Global temperature change potential (GTP) and surface temperature response.

Science.gov (United States)

Kumari, Shilpi; Hiloidhari, Moonmoon; Kumari, Nisha; Naik, S N; Dahiya, R P

2018-01-01

Two climate metrics, Global surface Temperature Change Potential (GTP) and the Absolute GTP (AGTP) are used for studying the global surface temperature impact of CH 4 emission from livestock in India. The impact on global surface temperature is estimated for 20 and 100 year time frames due to CH 4 emission. The results show that the CH 4 emission from livestock, worked out to 15.3 Tg in 2012. In terms of climate metrics GTP of livestock-related CH 4 emission in India in 2012 were 1030 Tg CO 2 e (GTP 20 ) and 62 Tg CO 2 e (GTP 100 ) at the 20 and 100 year time horizon, respectively. The study also illustrates that livestock-related CH 4 emissions in India can cause a surface temperature increase of up to 0.7mK and 0.036mK over the 20 and 100 year time periods, respectively. The surface temperature response to a year of Indian livestock emission peaks at 0.9mK in the year 2021 (9 years after the time of emission). The AGTP gives important information in terms of temperature change due to annual CH 4 emissions, which is useful when comparing policies that address multiple gases. Copyright © 2017 Elsevier Inc. All rights reserved.

What affects CH4/CO2 ratio in cow’s breath

DEFF Research Database (Denmark)

Hellwing, Anne Louise Frydendahl; Weisbjerg, Martin Riis; Madsen, Jørgen

2013-01-01

under farm management control. CO2 is released largely from microbial decay or burning of plant litter and soil organic matter. CH4 is produced when organic materials decompose under anoxic conditions, notably from fermentative digestion by ruminant livestock, stored manures, wetlands and rice grown...

Experimental measurements of vapor-liquid equilibria of the H2O + CO2 + CH4 ternary system

Science.gov (United States)

Qin, J.; Rosenbauer, R.J.; Duan, Zhenhao

2008-01-01

Reported are the experimental measurements on vapor-liquid equilibria in the H2O + CO2 + CH4 ternary system at temperatures from (324 to 375) K and pressures from (10 to 50) MPa. The results indicate that the CH4 solubility in the ternary mixture is about 10 % to 40 % more than that calculated by interpolation from the Henry's law constants of the binary system, H2O + CH4, and the solubility of CO2 is 6 % to 20 % more than what is calculated by the interpolation from the Henry's law constants of the binary mixture, H 2O + CO2. ?? 2008 American Chemical Society.

Expanding Spatial and Temporal Coverage of Arctic CH4 and CO2 Fluxes

Science.gov (United States)

Murphy, P.; Oechel, W. C.; Moreaux, V.; Losacco, S.; Zona, D.

2013-12-01

Carbon storage and exchange in Arctic ecosystems is the subject of intensive study focused on determining rates, controls, and mechanisms of CH4 and CO2 fluxes. The Arctic contains more than 1 Gt of Carbon in the upper meter of soil, both in the active layer and permafrost (Schuur et al., 2008; Tarnocai et al., 2009). However, the annual pattern and controls on the release of CH4 is inadequately understood in Arctic tundra ecosystems. Annual methane budgets are poorly understood, and very few studies measure fluxes through the freeze-up cycle during autumn months (Mastepanov et al., 2008; Mastepanov et al., 2010; Sturtevant et al., 2012). There is no known, relatively continuous, CH4 flux record for the Arctic. Clearly, the datasets that currently exist for budget calculations and model parameterization and verification are inadequate. This is likely due to the difficult nature of flux measurements in the Arctic. In September 2012, we initiated a research project towards continuous methane flux measurements along a latitudinal transect in Northern Alaska. The eddy-covariance (EC) technique is challenging in such extreme weather conditions due to the effects of ice formation and precipitation on instrumentation, including gas analyzers and sonic anemometers. The challenge is greater in remote areas of the Arctic, when low power availability and limited communication can lead to delays in data retrieval or data loss. For these reasons, a combination of open- and closed-path gas analyzers, and several sonic anemometers (including one with heating), have been installed on EC towers to allow for cross-comparison and cross-referencing of calculated fluxes. Newer instruments for fast CH4 flux determination include: the Los Gatos Research Fast Greenhouse Gas Analyzer and the Li-Cor LI-7700. We also included the self-heated Metek Class-A uSonic-3 Anemometer as a new instrument. Previously existing instruments used for comparison include the Li-Cor LI-7500; Li-Cor LI-7200

Fluid properties control degassing or storage of abiogenic CH4 during slab exhumation: the fluid inclusion record from the Western Alps.

Science.gov (United States)

Ferrando, S.; Castelli, D.; Frezzotti, M. L.

2017-12-01

Abiogenic CH4 can be produced by interaction between carbonates and reducing fluids derived from the hydration of ultramafics (e.g., mantle peridotite or HP Ol-serpentinite). This process occurs during slab exhumation because cooling promotes serpentinization of olivine in presence of water (Fo + H2O = Atg + Brc and the linked reactions: Fa + H2O = Fe-Atg + Mag + H2 and Atg + CaCO3 + H2 = Di + Brc + CH4 + H2O) at ca. 500-375°C (P=2.0-0.2 GPa). Experiments in the CH4-H2O-NaCl system indicate that, at these conditions, fluids are immiscible even for very low salinity (ca. 3 wt%) and that the NaCl content in the aqueous part of the fluid increases with temperature whereas the CH4 content in the gaseous part shows an opposite trend (Lamb et al., 2002; Li, 2017).In HP rodingite from the Piemonte ophiolite Zone (W Alps), primary fluid inclusions consisting of a brine (6 wt% CaCl2 + 6 wt% NaCl) with H2 + CH4 ≤ 1 mol % [CH4/(H2+CH4) = 0.37-10] occur in vesuvianite veins that formed at P=0.2 GPa and T=375°C. We interpret them as the aqueous part of an immiscible reducing fluid produced during late Alpine serpentinization of the surrounding ultramafics. Interestingly, CH4-H2 gaseous fluids are never reported in rodingite, whereas early CH4-H2O-H2±graphite and CH4-H2±graphite fluid inclusions, with variable gas-water proportions, trapped in calcite at P≤1.0 GPa and T≤450°C, are recently reported from HP "graphitized" ophicarbonate from the Lanzo peridotite Massif (W Alps; Vitale Brovarone et al., 2017).Both HP ophiolites and partially-serpentinized peridotite massifs are, thus, efficient lithologies to produce CH4 during exhumation. The amount of released CH4 depends on the amount of water available during exhumation. However, when fluids immiscibility occurs, the gaseous-rich part (CH4-H2) of the immiscible fluid produced in ultramafics likely remains confined in the slab because it is less mobile with respect to the aqueous-rich part due to its high dihedral

Hot filament-dissociation of (CH3)3SiH and (CH3)4Si, probed by vacuum ultra violet laser time of flight mass spectroscopy.

Science.gov (United States)

Sharma, Ramesh C; Koshi, Mitsuo

2006-11-01

The decomposition of trimethylsilane and tetramethylsilane has been investigated for the first time, using hot wire (catalytic) at various temperatures. Trimethylsilane is catalytic-dissociated in these species SiH(2), CH(3)SiH, CH(3), CH(2)Si. Time of flight mass spectroscopy signal of these species are linearly increasing with increasing catalytic-temperature. Time of flight mass spectroscopy (TOFMS) signals of (CH(3))(3)SiH and photodissociated into (CH(3))(2)SiH are decreasing with increasing hot filament temperature. TOFMS signal of (CH(3))(4)Si is decreasing with increasing hot wire temperature, but (CH(3))(3)Si signal is almost constant with increasing the temperature. We calculated activation energies of dissociated species of the parental molecules for fundamental information of reaction kinetics for the first time. Catalytic-dissociation of trimethylsilane, and tetramethylsilane single source time of flight coupled single photon VUV (118 nm) photoionization collisionless radicals at temperature range of tungsten filament 800-2360 K. The study is focused to understand the fundamental information on reaction kinetics of these molecules at hot wire temperature, and processes of catalytic-chemical vapour deposition (Cat-CVD) technique which could be implemented in amorphous and crystalline SiC semiconductors thin films.

[CH4 emission features of leading super-rice varieties and their relationships with the varieties growth characteristics in Yangtze Delta of China].

Science.gov (United States)

Yan, Xiao-Jun; Wang, Li-Li; Jiang, Yu; Deng, Ai-Xing; Tian, Yun-Lu; Zhang, Wei-Jian

2013-09-01

A pot experiment was conducted to study the CH4 emission features of fourteen leading super-rice varieties (six Japonica rice varieties and eight Indica hybrid rice varieties) and their relationships with the varieties growth characteristics in Yangtze Delta. Two distinct peaks of CH4 emission were detected during the entire growth period of the varieties, one peak occurred at full-tillering stage, and the other appeared at booting stage. The average total CH4 emission of Japonica rice varieties was 37.6% higher than that of the Indica hybrid rice varieties (Price types occurred at the post-anthesis phase. For all the varieties, there was a significant positive correlation between the total CH4 emission and the maximum leaf area, but the correlations between the CH4 emission and the other growth characteristics varied with variety type. The total CH4 emission of Japonica rice varieties had a significant positive correlation with plant height, while the correlations between the total CH4 emission of Indica hybrid rice varieties and their plant height were not significant. The total CH4 emission of Indica hybrid rice varieties had significant negative correlations with the total aboveground biomass, grain yield, and harvest index, but the correlations were not significant for Japonica rice varieties. The lower CH4 emission of Indica hybrid rice varieties was likely due to their significantly higher root biomass, as compared with Japonica rice varieties.

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2007-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2006-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2005-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2004-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2008-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-09-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-05-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-02-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-01-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codesand corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-12-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-01-18

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2004-10-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-03-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-09-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2004-12-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-11-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-12-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-01-30

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-06-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

Presumed PDF modeling of microjet assisted CH4–H2/air turbulent flames

International Nuclear Information System (INIS)

Chouaieb, Sirine; Kriaa, Wassim; Mhiri, Hatem; Bournot, Philippe

2016-01-01

Highlights: • Microjet assisted CH 4 –H 2 /air turbulent flames are numerically investigated. • Temperature, species and soot are well predicted by the Presumed PDF model. • An inner flame is identified due to the microjet presence. • The addition of hydrogen to the microjet assisted flames enhances mixing. • Soot emission is reduced by 36% for a 10% enriched microjet assisted flame. - Abstract: The characteristics of microjet assisted CH 4 –H 2 /air flames in a turbulent mode are numerically investigated. Simulations are performed using the Computational Fluid Dynamics code Fluent. The Presumed PDF and the Discrete Ordinates models are considered respectively for combustion and radiation modeling. The k–ε Realizable model is adopted as a turbulence closure model. The Tesner model is used to calculate soot particle quantities. In the first part of this paper, the Presumed PDF model is compared to the Eddy Dissipation model and to slow chemistry combustion models from literature. Results show that the Presumed PDF model predicts correctly thermal and species fields, as well as soot formation. The effect of hydrogen enrichment on CH 4 /air confined flames under the addition of an air microjet is investigated in the second part of this work. The found results show that an inner flame was identified due to the air microjet for the CH 4 –H 2 /air flames. Moreover, the increase of hydrogen percentage in the fuel mixture leads to mixing enhancement and consequently to considerable soot emission reduction.

Inverse modelling of national and European CH4 emissions using the atmospheric zoom model TM5

Directory of Open Access Journals (Sweden)

P. Bergamaschi

2005-01-01

Full Text Available A synthesis inversion based on the atmospheric zoom model TM5 is used to derive top-down estimates of CH4 emissions from individual European countries for the year 2001. We employ a model zoom over Europe with 1° × 1° resolution that is two-way nested into the global model domain (with resolution of 6° × 4°. This approach ensures consistent boundary conditions for the zoom domain and thus European top-down estimates consistent with global CH4 observations. The TM5 model, driven by ECMWF analyses, simulates synoptic scale events at most European and global sites fairly well, and the use of high-frequency observations allows exploiting the information content of individual synoptic events. A detailed source attribution is presented for a comprehensive set of 56 monitoring sites, assigning the atmospheric signal to the emissions of individual European countries and larger global regions. The available observational data put significant constraints on emissions from different regions. Within Europe, in particular several Western European countries are well constrained. The inversion results suggest up to 50-90% higher anthropogenic CH4 emissions in 2001 for Germany, France and UK compared to reported UNFCCC values (EEA, 2003. A recent revision of the German inventory, however, resulted in an increase of reported CH4 emissions by 68.5% (EEA, 2004, being now in very good agreement with our top-down estimate. The top-down estimate for Finland is distinctly smaller than the a priori estimate, suggesting much smaller CH4 emissions from Finnish wetlands than derived from the bottom-up inventory. The EU-15 totals are relatively close to UNFCCC values (within 4-30% and appear very robust for different inversion scenarios.

CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

KAUST Repository

Tingas, Efstathios Al.; Manias, Dimitris M.; Sarathy, Mani; Goussis, Dimitris A.

2018-01-01

Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53

Development of a method for estimating total CH{sub 4} emission from rice paddies in Japan using the DNDC-Rice model

Energy Technology Data Exchange (ETDEWEB)

Katayanagi, Nobuko [National Institute for Agro-Environmental Sciences, 3-1-3 Kannondai, Tsukuba, Ibaraki 305-8604 (Japan); Fumoto, Tamon, E-mail: tamon@affrc.go.jp [National Institute for Agro-Environmental Sciences, 3-1-3 Kannondai, Tsukuba, Ibaraki 305-8604 (Japan); Hayano, Michiko [National Institute for Agro-Environmental Sciences, 3-1-3 Kannondai, Tsukuba, Ibaraki 305-8604 (Japan); Kyushu Okinawa Agricultural Research Center, National Agriculture and Food Research Organization, Anno 1742-1, Nishinoomote, Kagoshima 891-3102 (Japan); Takata, Yusuke; Kuwagata, Tsuneo; Shirato, Yasuhito [National Institute for Agro-Environmental Sciences, 3-1-3 Kannondai, Tsukuba, Ibaraki 305-8604 (Japan); Sawano, Shinji [Forestry and Forest Products Research Institute (FFPRI), 1 Matsunosato, Tsukuba, Ibaraki 305-8687 (Japan); Kajiura, Masako; Sudo, Shigeto; Ishigooka, Yasushi; Yagi, Kazuyuki [National Institute for Agro-Environmental Sciences, 3-1-3 Kannondai, Tsukuba, Ibaraki 305-8604 (Japan)

2016-03-15

Methane (CH{sub 4}) is a greenhouse gas, and paddy fields are one of its main anthropogenic emission sources. To mitigate this emission based on effective management measures, CH{sub 4} emission from paddy fields must be quantified at a national scale. In Japan, country-specific emission factors have been applied since 2003 to estimate national CH{sub 4} emission from paddy fields. However, this method cannot account for the effects of weather conditions and temporal variability of nitrogen fertilizer and organic matter application rates; thus, the estimated emission is highly uncertain. To improve the accuracy of national-scale estimates, we calculated country-specific emission factors using the DeNitrification–DeComposition-Rice (DNDC-Rice) model. First, we calculated CH{sub 4} emission from 1981 to 2010 using 986 datasets that included soil properties, meteorological data, and field management data. Using the simulated site-specific emission, we calculated annual mean emission for each of Japan's seven administrative regions, two water management regimes (continuous flooding and conventional mid-season drainage), and three soil drainage rates (slow, moderate, and fast). The mean emission was positively correlated with organic carbon input to the field, and we developed linear regressions for the relationships among the regions, water management regimes, and drainage rates. The regression results were within the range of published observation values for site-specific relationships between CH{sub 4} emission and organic carbon input rates. This suggests that the regressions provide a simplified method for estimating CH{sub 4} emission from Japanese paddy fields, though some modifications can further improve the estimation accuracy. - Highlights: • DNDC-Rice is a process-based model to simulate rice CH{sub 4} emission from rice paddies. • We simulated annual CH{sub 4} emissions from 986 paddy fields in Japan by DNDC-Rice. • Regional means of CH{sub 4

Influence of meteorology and interrelationship with greenhouse gases (CO2 and CH4) at a sub-urban site of India

Science.gov (United States)

Sreenivas, G.; Mahesh, P.; Subin, J.; Kanchana, A. L.; Rao, P. V. N.; Dadhwal, V. K.

2015-12-01

Atmospheric greenhouse gases (GHGs) such as carbon dioxide (CO2) and methane (CH4) are important climate forcing agents due to their significant impact on the climate system. The present study brings out first continuous measurements of atmospheric GHG's using high precision Los Gatos Research's-greenhouse gas analyser (LGR-GGA) over Shadnagar, a suburban site of Central India during the period 2014. The annual mean of CO2 and CH4 over the study region is found to be 394 ± 2.92 and 1.92 ± 0.07 ppm (mean, μ ± 1 SD, σ) respectively. CO2 and CH4 showed a significant seasonal variation during the study period with maximum (minimum) CO2 observed during Pre-monsoon (Monsoon), while CH4 recorded maximum during post-monsoon and minimum in monsoon. A consistent diurnal mixing ratio of these gases is observed with high (low) during night (afternoon) hours throughout the study period. Influences of prevailing meteorology (air temperature, wind speed, wind direction and relative humidity) on GHG's have also been investigated. CO2 and CH4 showed a strong positive correlation during winter, pre-monsoon, monsoon and post-monsoon with R equal to 0.80, 0.80, 0.61 and 0.72 respectively. It implies the seasonal variations in source-sink mechanisms of CO2 and CH4. Present study also confirms implicitly the presence OH radicals as a major sink of CH4 over the study region.

Time-series measurements of methane (CH4) distribution during open water and ice-cover in lakes throughout the Mackenzie River Delta (Canada)

Science.gov (United States)

McIntosh, H.; Lapham, L.; Orcutt, B.; Wheat, C. G.; Lesack, L.; Bergstresser, M.; Dallimore, S. R.; MacLeod, R.; Cote, M.

2016-12-01

Arctic lakes are known to emit large amounts of methane to the atmosphere and their importance to the global methane (CH4) cycle has been recognized. It is well known CH4 builds up in Arctic lakes during ice-cover, but the amount of and when the CH4 is released to the atmosphere is not well known. Our preliminary results suggest the largest flux of CH4 from lakes to the atmosphere occurs slightly before complete ice-out; while others have shown the largest flux occurs when lakes overturn in the spring. During ice-out, CH4 can also be oxidized by methane oxidizing bacteria before it can efflux to the atmosphere from the surface water. In order to elucidate the processes contributing to Arctic lake CH4 emissions, continuous, long-term and large scale spatial sampling is required; however it is difficult to achieve in these remote locations. We address this problem using two sampling techniques. 1) We deployed osmotically powered pumps (OsmoSamplers), which were able to autonomously and continuously collect lake bottom water over the course of a year from multiple lakes in the Mackenzie River Delta. OsmoSamplers were placed in four lakes in the mid Delta near Inuvik, Northwest Territories, Canada, two lakes in the outer Delta, and two coastal lakes on Richard's Island in 2015. The dissolved CH4 concentration, stable isotope content of CH4 (δ13C-CH4), and dissolved sulfate concentrations in bottom water from these lakes will be presented to better understand methane dynamics under the ice and over time. 2) Along with the time-series data, we will also present data from discrete samples collected from 40 lakes in the mid Delta during key time periods, before and immediately after the spring ice-out. By determining the CH4 dynamics throughout the year we hope to improve predictions of how CH4 emissions may change in a warming Arctic environment.

F-state quenching with CH4 for buffer-gas cooled 171Y b+ frequency standard

Directory of Open Access Journals (Sweden)

Y.-Y. Jau

2015-11-01

Full Text Available We report that methane, CH4, 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 × 106 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 × 105 s−1 Torr−1. In our buffer-gas cooled 171Y b+ microwave clock system, we find that only ≤10−8 Torr of CH4 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.

A simple calculation algorithm to separate high-resolution CH4 flux measurements into ebullition and diffusion-derived components

Science.gov (United States)

Hoffmann, Mathias; Schulz-Hanke, Maximilian; Garcia Alba, Joana; Jurisch, Nicole; Hagemann, Ulrike; Sachs, Torsten; Sommer, Michael; Augustin, Jürgen

2016-04-01

Processes driving methane (CH4) emissions in wetland ecosystems are highly complex. Especially, the separation of CH4 emissions into ebullition and diffusion derived flux components, a perquisite for the mechanistic process understanding and identification of potential environmental driver is rather challenging. We present a simple calculation algorithm, based on an adaptive R-script, which separates open-water, closed chamber CH4 flux measurements into diffusion- and ebullition-derived components. Hence, flux component specific dynamics are revealed and potential environmental driver identified. Flux separation is based on a statistical approach, using ebullition related sudden concentration changes obtained during high resolution CH4 concentration measurements. By applying the lower and upper quartile ± the interquartile range (IQR) as a variable threshold, diffusion dominated periods of the flux measurement are filtered. Subsequently, flux calculation and separation is performed. The algorithm was verified in a laboratory experiment and tested under field conditions, using flux measurement data (July to September 2013) from a flooded, former fen grassland site. Erratic ebullition events contributed 46% to total CH4 emissions, which is comparable to values reported by literature. Additionally, a shift in the diurnal trend of diffusive fluxes throughout the measurement period, driven by the water temperature gradient, was revealed.

Soil-atmospheric exchange of CO2, CH4, and N2O in three subtropical forest ecosystems in southern China

Science.gov (United States)

Tang, X.; Liu, S.; Zhou, G.; Zhang, Dongxiao; Zhou, C.

2006-01-01

The magnitude, temporal, and spatial patterns of soil-atmospheric greenhouse gas (hereafter referred to as GHG) exchanges in forests near the Tropic of Cancer are still highly uncertain. To contribute towards an improvement of actual estimates, soil-atmospheric CO2, CH4, and N2O fluxes were measured in three successional subtropical forests at the Dinghushan Nature Reserve (hereafter referred to as DNR) in southern China. Soils in DNR forests behaved as N2O sources and CH4 sinks. Annual mean CO2, N2O, and CH4 fluxes (mean ?? SD) were 7.7 ?? 4.6MgCO2-Cha-1 yr-1, 3.2 ?? 1.2 kg N2ONha-1 yr-1, and 3.4 ?? 0.9 kgCH4-Cha-1 yr-1, respectively. The climate was warm and wet from April through September 2003 (the hot-humid season) and became cool and dry from October 2003 through March 2004 (the cool-dry season). The seasonality of soil CO2 emission coincided with the seasonal climate pattern, with high CO2 emission rates in the hot-humid season and low rates in the cool-dry season. In contrast, seasonal patterns of CH4 and N2O fluxes were not clear, although higher CH4 uptake rates were often observed in the cool-dry season and higher N2O emission rates were often observed in the hot-humid season. GHG fluxes measured at these three sites showed a clear increasing trend with the progressive succession. If this trend is representative at the regional scale, CO2 and N2O emissions and CH4 uptake in southern China may increase in the future in light of the projected change in forest age structure. Removal of surface litter reduced soil CO2 effluxes by 17-44% in the three forests but had no significant effect on CH4 absorption and N2O emission rates. This suggests that microbial CH4 uptake and N2O production was mainly related to the mineral soil rather than in the surface litter layer. ?? 2006 Blackwell Publishing Ltd.

Tunneling in the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H reaction and its isotopic analog: an anomalous isotope effect

Energy Technology Data Exchange (ETDEWEB)

Kurosaki, Yuzuru; Takayanagi, Toshiyuki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1998-10-01

Vibrationally adiabatic ground-state potential curves for the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H (I) and CD{sub 3} + H{sub 2} {yields} CD{sub 4}H + H (II) reactions were obtained by adding zero-point energies of harmonic vibrations orthogonal to intrinsic reaction coordinate (IRC) to bare potential curves along IRC. It was clarified that both the barrier height and barrier width of reaction II are smaller than those of reaction I. This computational result qualitatively explains the experimental observation of Momose et al. (J. Chem. Phys. 108 (1998) 7334) that reaction II occurs but reaction I does not occur in solid parahydrogen at 5 K. (author)

Inverse modeling of GOSAT-retrieved ratios of total column CH4 and CO2 for 2009 and 2010

Directory of Open Access Journals (Sweden)

S. Pandey

2016-04-01

Full Text Available This study investigates the constraint provided by greenhouse gas measurements from space on surface fluxes. Imperfect knowledge of the light path through the atmosphere, arising from scattering by clouds and aerosols, can create biases in column measurements retrieved from space. To minimize the impact of such biases, ratios of total column retrieved CH4 and CO2 (Xratio have been used. We apply the ratio inversion method described in Pandey et al. (2015 to retrievals from the Greenhouse Gases Observing SATellite (GOSAT. The ratio inversion method uses the measured Xratio as a weak constraint on CO2 fluxes. In contrast, the more common approach of inverting proxy CH4 retrievals (Frankenberg et al., 2005 prescribes atmospheric CO2 fields and optimizes only CH4 fluxes. The TM5–4DVAR (Tracer Transport Model version 5–variational data assimilation system inverse modeling system is used to simultaneously optimize the fluxes of CH4 and CO2 for 2009 and 2010. The results are compared to proxy inversions using model-derived CO2 mixing ratios (XCO2model from CarbonTracker and the Monitoring Atmospheric Composition and Climate (MACC Reanalysis CO2 product. The performance of the inverse models is evaluated using measurements from three aircraft measurement projects. Xratio and XCO2model are compared with TCCON retrievals to quantify the relative importance of errors in these components of the proxy XCH4 retrieval (XCH4proxy. We find that the retrieval errors in Xratio (mean  =  0.61 % are generally larger than the errors in XCO2model (mean  =  0.24 and 0.01 % for CarbonTracker and MACC, respectively. On the annual timescale, the CH4 fluxes from the different satellite inversions are generally in agreement with each other, suggesting that errors in XCO2model do not limit the overall accuracy of the CH4 flux estimates. On the seasonal timescale, however, larger differences are found due to uncertainties in XCO2model, particularly

High net CO2 and CH4 release at a eutrophic shallow lake on a formerly drained fen

Science.gov (United States)

Franz, Daniela; Koebsch, Franziska; Larmanou, Eric; Augustin, Jürgen; Sachs, Torsten

2016-05-01

Drained peatlands often act as carbon dioxide (CO2) hotspots. Raising the groundwater table is expected to reduce their CO2 contribution to the atmosphere and revitalise their function as carbon (C) sink in the long term. Without strict water management rewetting often results in partial flooding and the formation of spatially heterogeneous, nutrient-rich shallow lakes. Uncertainties remain as to when the intended effect of rewetting is achieved, as this specific ecosystem type has hardly been investigated in terms of greenhouse gas (GHG) exchange. In most cases of rewetting, methane (CH4) emissions increase under anoxic conditions due to a higher water table and in terms of global warming potential (GWP) outperform the shift towards CO2 uptake, at least in the short term.Based on eddy covariance measurements we studied the ecosystem-atmosphere exchange of CH4 and CO2 at a shallow lake situated on a former fen grassland in northeastern Germany. The lake evolved shortly after flooding, 9 years previous to our investigation period. The ecosystem consists of two main surface types: open water (inhabited by submerged and floating vegetation) and emergent vegetation (particularly including the eulittoral zone of the lake, dominated by Typha latifolia). To determine the individual contribution of the two main surface types to the net CO2 and CH4 exchange of the whole lake ecosystem, we combined footprint analysis with CH4 modelling and net ecosystem exchange partitioning.The CH4 and CO2 dynamics were strikingly different between open water and emergent vegetation. Net CH4 emissions from the open water area were around 4-fold higher than from emergent vegetation stands, accounting for 53 and 13 g CH4 m-2 a-1 respectively. In addition, both surface types were net CO2 sources with 158 and 750 g CO2 m-2 a-1 respectively. Unusual meteorological conditions in terms of a warm and dry summer and a mild winter might have facilitated high respiration rates. In sum, even after 9

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

Science.gov (United States)

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.

New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes.

Science.gov (United States)

Gilbert-Wilson, Ryan; Field, Leslie D; Bhadbhade, Mohan M

2012-03-05

The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.

Carbonate control of H2 and CH4 production in serpentinization systems at elevated P-Ts

Science.gov (United States)

Jones, L. Camille; Rosenbauer, Robert; Goldsmith, Jonas I.; Oze, Christopher

2010-01-01

Serpentinization of forsteritic olivine results in the inorganic synthesis of molecular hydrogen (H2) in ultramafic hydrothermal systems (e.g., mid-ocean ridge and forearc environments). Inorganic carbon in those hydrothermal systems may react with H2 to produce methane (CH4) and other hydrocarbons or react with dissolved metal ions to form carbonate minerals. Here, we report serpentinization experiments at 200°C and 300 bar demonstrating Fe2+ being incorporated into carbonates more rapidly than Fe2+ oxidation (and concomitant H2 formation) leading to diminished yields of H2 and H2-dependent CH4. In addition, carbonate formation is temporally fast in carbonate oversaturated fluids. Our results demonstrate that carbonate chemistry ultimately modulates the abiotic synthesis of both H2 and CH4 in hydrothermal ultramafic systems and that ultramafic systems present great potential for CO2-mineral sequestration.

Influence of vehicular emissions on atmospheric CH4 and NMHC mixing ratios and its correlation with CO and other VOCs tracers in Mexico City

Science.gov (United States)

Solano-Murillo, M.; Torres-Jardón, R.; Ruiz-Suárez, L. G.; Barrera-Huertas, H.; Hernandez-Solis, J. M.

2016-12-01

The Mexico City Metropolitan Area (MCMA) is one of the world's largest and most polluted urban areas. A recent GHC emission inventory for MCMA suggests that vehicular emissions contribute with around 37% of CH4, followed by landfills and dump garbage areas (30%) and construction and manufacturing (27%). Contrary to other urban areas, natural gas is not the main fuel used in MCMA, neither for domestic and industrial heating, nor for transportation. Therefore, there is a great uncertainty about who is the main contributor of CH4 emissions. An intensive monitoring campaign of methane (CH4), Non-methane hydrocarbons (NMHC) and carbon monoxide (CO) was performed between February and March 2015 in southwest MCMA. Methane concentrations showed sometimes a diurnal pattern similar to those of CO and to NMHC but most of the time this similarity was lost (CH4 vs CO, R2 = 0.27; CH4 vs NMHC, R2 = 0.28). However, NMHC correlated well with CO (R2 = 0.75). The intercepts of the CH4-CO correlation resulted in [CH4] 1.8 ppm and that of the CO-NMHC correlation in [CO] 0.080 ppb. The lack of agreement between CH4 and CO indicates these species do not come from the same sources. The results suggest that vehicular emissions are not significant contributors to atmospheric CH4 and that the background methane concentration has not change significantly in 25 years. An attempt to correlate some tracers COVs tracers of vehicular and biomass burning with CH4, NMHC and CH4 is done.

New accurate theoretical line lists of 12CH4 and 13CH4 in the 0-13400 cm-1 range: Application to the modeling of methane absorption in Titan's atmosphere

Science.gov (United States)

Rey, Michaël; Nikitin, Andrei V.; Bézard, Bruno; Rannou, Pascal; Coustenis, Athena; Tyuterev, Vladimir G.

2018-03-01

The spectrum of methane is very important for the analysis and modeling of Titan's atmosphere but its insufficient knowledge in the near infrared, with the absence of reliable absorption coefficients, is an important limitation. In order to help the astronomer community for analyzing high-quality spectra, we report in the present work the first accurate theoretical methane line lists (T = 50-350 K) of 12CH4 and 13CH4 up to 13400 cm-1 ( > 0.75 μm). These lists are built from extensive variational calculations using our recent ab initio potential and dipole moment surfaces and will be freely accessible via the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru). Validation of these lists is presented throughout the present paper. For the sample of lines where upper energies were available from published analyses of experimental laboratory 12CH4 spectra, small empirical corrections in positions were introduced that could be useful for future high-resolution applications. We finally apply the TheoRetS line list to model Titan spectra as observed by VIMS and by DISR, respectively onboard Cassini and Huygens. These data are used to check that the TheoReTS line lists are able to model observations. We also make comparisons with other experimental or theoretical line lists. It appears that TheoRetS gives very reliable results better than ExoMol and even than HITRAN2012, except around 1.6 μm where it gives very similar results. We conclude that TheoReTS is suitable to be used for the modeling of planetary radiative transfer and photometry. A re-analysis of spectra recorded by the DISR instrument during the descent of the Huygens probe suggests that the CH4 mixing ratio decreases with altitude in Titan's stratosphere, reaching a value of ∼10-2 above the 110 km altitude.

Influence of Meteorology and interrelationship with greenhouse gases (CO2 and CH4) at a suburban site of India

Science.gov (United States)

Sreenivas, Gaddamidi; Mahesh, Pathakoti; Subin, Jose; Lakshmi Kanchana, Asuri; Venkata Narasimha Rao, Pamaraju; Dadhwal, Vinay Kumar

2016-03-01

Atmospheric greenhouse gases (GHGs), such as carbon dioxide (CO2) and methane (CH4), are important climate forcing agents due to their significant impacts on the climate system. The present study brings out first continuous measurements of atmospheric GHGs using high-precision LGR-GGA over Shadnagar, a suburban site of Central India during the year 2014. The annual mean CO2 and CH4 over the study region are found to be 394 ± 2.92 and 1.92 ± 0.07 ppm (μ ± 1σ) respectively. CO2 and CH4 show a significant seasonal variation during the study period with maximum (minimum) CO2 observed during pre-monsoon (monsoon), while CH4 recorded the maximum during post-monsoon and minimum during monsoon. Irrespective of the seasons, consistent diurnal variations of these gases are observed. Influences of prevailing meteorology (air temperature, wind speed, wind direction, and relative humidity) on GHGs have also been investigated. CO2 and CH4 show a strong positive correlation during winter, pre-monsoon, monsoon, and post-monsoon with correlation coefficients (Rs) equal to 0.80, 0.80, 0.61, and 0.72 respectively, indicating a common anthropogenic source for these gases. Analysis of this study reveals the major sources for CO2 are soil respiration and anthropogenic emissions while vegetation acts as a main sink, whereas the major source and sink for CH4 are vegetation and presence of hydroxyl (OH) radicals.

Phosphorus addition mitigates N2O and CH4 emissions in N-saturated subtropical forest, SW China

Directory of Open Access Journals (Sweden)

L. Yu

2017-06-01

Full Text Available Chronically elevated nitrogen (N deposition has led to severe nutrient imbalance in forest soils. Particularly in tropical and subtropical forest ecosystems, increasing N loading has aggravated phosphorus (P limitation of biomass production, and has resulted in elevated emissions of nitrous oxide (N2O and reduced uptake of methane (CH4, both of which are important greenhouse gases. Yet, the interactions of N and P and their effects on greenhouse gas emissions remain elusive. Here, we report N2O and CH4 emissions together with soil N and P data for a period of 18 months following a single P addition (79 kg P ha−1, as NaH2PO4 powder to an N-saturated, Masson pine-dominated forest soil at TieShanPing (TSP, Chongqing, south-western (SW China. We observed a significant decline in both nitrate (NO3− concentrations in soil water (5 and 20 cm depths and in soil N2O emissions, following P application. We hypothesise that enhanced N uptake by plants in response to P addition, resulted in less available NO3− for denitrification. By contrast to most other forest ecosystems, TSP is a net source of CH4. P addition significantly decreased CH4 emissions and turned the soil from a net source into a net sink. Based on our observation and previous studies in South America and China, we believe that P addition relieves N inhibition of CH4 oxidation. Within the 1.5 years after P addition, no significant increase of forest growth was observed and P stimulation of forest N uptake by understorey vegetation remains to be confirmed. Our study indicates that P fertilisation of N-saturated, subtropical forest soils may mitigate N2O and CH4 emissions, in addition to alleviating nutrient imbalances and reducing losses of N through NO3− leaching.

Transport and transformation of soil-derived CO2, CH4 and DOC sustain CO2 supersaturation in small boreal streams.

Science.gov (United States)

Rasilo, Terhi; Hutchins, Ryan H S; Ruiz-González, Clara; Del Giorgio, Paul A

2017-02-01

Streams are typically supersaturated in carbon dioxide (CO 2 ) and methane (CH 4 ), and are recognized as important components of regional carbon (C) emissions in northern landscapes. Whereas there is consensus that in most of the systems the CO 2 emitted by streams represents C fixed in the terrestrial ecosystem, the pathways delivering this C to streams are still not well understood. We assessed the contribution of direct soil CO 2 injection versus the oxidation of soil-derived dissolved organic C (DOC) and CH 4 in supporting CO 2 supersaturation in boreal streams in Québec. We measured the concentrations of CO 2 , CH 4 and DOC in 43 streams and adjacent soil waters during summer base-flow period. A mass balance approach revealed that all three pathways are significant, and that the mineralization of soil-derived DOC and CH 4 accounted for most of the estimated stream CO 2 emissions (average 75% and 10%, respectively), and that these estimated contributions did not change significantly between the studied low order (≤3) streams. Whereas some of these transformations take place in the channel proper, our results suggest that they mainly occur in the hyporheic zones of the streams. Our results further show that stream CH 4 emissions can be fully explained by soil CH 4 inputs. This study confirms that these boreal streams, and in particular their hyporheic zones, are extremely active processors of soil derived DOC and CH 4 , not just vents for soil produced CO 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

Reactions of 11C recoil atoms in the systems H2O-NH3, H2O-CH4 and NH3-CH4

International Nuclear Information System (INIS)

Nebeling, B.

1988-11-01

In this study the chemical reactions of recoil carbon 11 in the binary gas mixtures H 2 O-NH 3 , H 2 O-CH 4 and NH 3 -CH 4 in different mixing ratios as well as in solid H 2 O and in a solid H 2 O-NH 3 mixture were analyzed in dependence of the dose. The analyses were to serve e.g. the simulation of chemical processes caused by solar wind, solar radiation and cosmic radiation in the coma and core of comets. They were to give further information about the role of the most important biogeneous element carbon, i.e. carbon, in the chemical evolution of the solar system. Besides the actual high energy processes resulting in the so-called primary products, also the radiation-chemical changes of the primary products were also observed in a wide range of dosing. The generation of the energetic 11 C atoms took place according to the target composition by the nuclear reactions 14 N(p,α) 11 C, 12 C( 3 He,α) 11 C or the 16 O(p,αpn) 11 C reaction. The identification of the products marked with 11 C was carried out by means of radio gas chromatography or radio liquid chromatography (HPLC). (orig./RB) [de

Prediction CH4 Emissions from the Wetlands in the Sanjiang Plain of Northeastern China in the 21st Century.

Directory of Open Access Journals (Sweden)

Tingting Li

Full Text Available The Sanjiang Plain has been experienced significant wetland loss due to expanded agricultural activities, and will be potentially restored by the China National Wetland Conservation Action Plan (NWCP in future. The objective of this study is to evaluate the impact of future climate warming and wetland restoration on wetland CH4 emissions in northeast China. We used an atmosphere-vegetation interaction model (AVIM2 to drive a modified biogeophysical model (CH4MODwetland, and projected CH4 flux variations from the Sanjiang Plain wetlands under different Representative Concentration Pathway scenarios throughout the 21st century. Model validation showed that the regressions between the observed and simulated CH4 fluxes by the modified model produced an R2 of 0.49 with a slope of 0.87 (p<0.001, n = 237. According to the AVIM2 simulation, the net primary productivity of the Sanjiang Plain wetlands will increase by 38.2 g m-2 yr-1, 116.6 g m-2 yr-1 and 250.4 g m-2 yr-1 under RCP 2.6, RCP 4.5 and RCP 8.5, respectively, by the end of this century. For RCP 2.6, 4.5 and 8.5 scenarios, the CH4 fluxes will increase by 5.7 g m-2 yr-1, 57.5 g m-2 yr-1 and 112.2 g m-2 yr-1. Combined with the wetland restoration, the regional emissions will increase by 0.18‒1.52 Tg. The CH4 emissions will be stimulated by climate change and wetland restoration. Regional wetland restoration planning should be directed against different climate scenarios in order to suppress methane emissions.

Process for the separation of contaminant or mixture of contaminants from a Ch4-comprising gaseous feed streem

NARCIS (Netherlands)

2012-01-01

The invention provides a process for the separation of a contaminant or mixture of contaminants from a CH4-comprising gaseous feed streem, comprising the subsequent steps of: a) passing a CH4-comprising gaseous feed streem comprising the contaminant or the mixture of contaminants in to and through a

Investigating the emission, dissolution, and oxidation of CH4 within and around a seep bubble plume in the Gulf of Mexico.

Science.gov (United States)

Leonte, M.; Kessler, J. D.; Socolofsky, S. A.

2016-02-01

One of the largest carbon reservoirs on the planet is stored as methane (CH4) in and below the seafloor. However, a large discrepancy exists between estimated fluxes of CH4 into the water column and CH4 fluxes from the sea surface to the atmosphere, suggesting that a significant fraction of CH4 released from seafloor seeps is dissolved and potentially removed through microbial oxidation. Here we present data investigating the fate of CH4 released from the Sleeping Dragon seep site in the Gulf of Mexico. The bubble plume was followed from the seafloor until it fully dissolved using a remotely operated vehicle (ROV). Water samples were collected by the ROV at different depths as well as lateral transects through the bubble plume. These samples were analyzed for dissolved concentrations of methane, ethane, propane, and butane as well as the 13C isotopic ratio of methane. Furthermore, seep bubbles from the seafloor were also collected and analyzed for the same properties. Based on these chemical data, the rate of CH4 emission from the seafloor, oxidation in the water column, and dissolution are investigated.

Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

Science.gov (United States)

Bourg, I. C.; Gadikota, G.; Dazas, B.

2016-12-01

Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

Science.gov (United States)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and

Mitigating CH4 and N2O emissions from intensive rice production systems in northern Vietnam

DEFF Research Database (Denmark)

Tariq, Azeem; Vu, Quynh Duong; Jensen, Lars Stoumann

2017-01-01

-growing seasons in northern Vietnam, to evaluate the effectiveness of drainage patterns on methane (CH4) and nitrous oxide (N2O) emissions under farmers’ variable conditions. Two improved drainage practices (pre-planting plus midseason [PM] drainage and early-season plus midseason [EM] drainage) were compared...... with local practices of water management (midseason drainage [M] and conventional continuous flooding (control) [C]) with full residue [F] and reduced residue [R] (local practice of residue management) incorporation. The GHG mitigation potential of water regimes was tested in two water management systems...... (efficient field water management [EWM] system and inefficient field water management [IWM] system). In EWM system, EM resulted an average 14% and 55% reduction in CH4 emissions compared to M with R and F respectively. The EM lowered the CH4 emissions by 67% and 43% compared to C in the EWM and IWM...

Reduced gas seepages in ophiolitic complexes: Evidences for multiple origins of the H2-CH4-N2 gas mixtures

Science.gov (United States)

Vacquand, Christèle; Deville, Eric; Beaumont, Valérie; Guyot, François; Sissmann, Olivier; Pillot, Daniel; Arcilla, Carlo; Prinzhofer, Alain

2018-02-01

This paper proposes a comparative study of reduced gas seepages occurring in ultrabasic to basic rocks outcropping in ophiolitic complexes based on the study of seepages from Oman, the Philippines, Turkey and New Caledonia. This study is based on analyses of the gas chemical composition, noble gases contents, stable isotopes of carbon, hydrogen and nitrogen. These seepages are mostly made of mixtures of three main components which are H2, CH4 and N2 in various proportions. The relative contents of the three main gas components show 4 distinct types of gas mixtures (H2-rich, N2-rich, N2-H2-CH4 and H2-CH4). These types are interpreted as reflecting different zones of gas generation within or below the ophiolitic complexes. In the H2-rich type, associated noble gases display signatures close to the value of air. In addition to the atmospheric component, mantle and crustal contributions are present in the N2-rich, N2-H2-CH4 and H2-CH4 types. H2-bearing gases are either associated with ultra-basic (pH 10-12) spring waters or they seep directly in fracture systems from the ophiolitic rocks. In ophiolitic contexts, ultrabasic rocks provide an adequate environment with available Fe2+ and alkaline conditions that favor H2 production. CH4 is produced either directly by reaction of dissolved CO2 with basic-ultrabasic rocks during the serpentinization process or in a second step by H2-CO2 interaction. H2 is present in the gas when no more carbon is available in the system to generate CH4. The N2-rich type is notably associated with relatively high contents of crustal 4He and in this gas type N2 is interpreted as issued mainly from sediments located below the ophiolitic units.

High-Throughput Computational Screening of the Metal Organic Framework Database for CH4/H2 Separations.

Science.gov (United States)

Altintas, Cigdem; Erucar, Ilknur; Keskin, Seda

2018-01-31

Metal organic frameworks (MOFs) have been considered as one of the most exciting porous materials discovered in the last decade. Large surface areas, high pore volumes, and tailorable pore sizes make MOFs highly promising in a variety of applications, mainly in gas separations. The number of MOFs has been increasing very rapidly, and experimental identification of materials exhibiting high gas separation potential is simply impractical. High-throughput computational screening studies in which thousands of MOFs are evaluated to identify the best candidates for target gas separation is crucial in directing experimental efforts to the most useful materials. In this work, we used molecular simulations to screen the most complete and recent collection of MOFs from the Cambridge Structural Database to unlock their CH 4 /H 2 separation performances. This is the first study in the literature, which examines the potential of all existing MOFs for adsorption-based CH 4 /H 2 separation. MOFs (4350) were ranked based on several adsorbent evaluation metrics including selectivity, working capacity, adsorbent performance score, sorbent selection parameter, and regenerability. A large number of MOFs were identified to have extraordinarily large CH 4 /H 2 selectivities compared to traditional adsorbents such as zeolites and activated carbons. We examined the relations between structural properties of MOFs such as pore sizes, porosities, and surface areas and their selectivities. Correlations between the heat of adsorption, adsorbility, metal type of MOFs, and selectivities were also studied. On the basis of these relations, a simple mathematical model that can predict the CH 4 /H 2 selectivity of MOFs was suggested, which will be very useful in guiding the design and development of new MOFs with extraordinarily high CH 4 /H 2 separation performances.

[(CH3)3NCH2CH2NH3]SnI4: a layered perovskite with quaternary/primary ammonium dications and short interlayer iodine-iodine contacts.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B; Medeiros, David R

2003-03-10

The organic-inorganic hybrid [(CH(3))(3)NCH(2)CH(2)NH(3)]SnI(4) presents a layered perovskite structure, templated by an organic dication containing both a primary and a quaternary ammonium group. Due to the high charge density and small size of the organic cation, the separation of the perovskite layers is small and short iodine-iodine contacts of 4.19 A are formed between the layers. Optical thin-film measurements on this compound indicate a significant red shift of the exciton peak (630 nm) associated with the band gap, as compared with other SnI(4)(2)(-)-based layered perovskite structures.

Reaction Dynamics of CH{sub 3} + HBr → CH{sub 4} + Br at 150-1000 K

Energy Technology Data Exchange (ETDEWEB)

Ree, Jongbaik [Chonnam National Univ., Gwangju (Korea, Republic of); Kim, Yoo Hang [Inha Univ., Incheon (Korea, Republic of); Shin, Hyung Kyu [Univ. of Nevado, Nevado (United States)

2013-08-15

The kinetics of the radical-polar molecule reaction CH{sub 3} + HBr → CH{sub 4} + Br has been studied at temperatures between 150 and 1000 K using classical dynamics procedures. Potential energy surfaces constructed using analytical forms of inter- and intramolecular interaction energies show a shallow well and barrier in the entrance channel, which affect the collision dynamics at low temperatures. Different collision models are used to distinguish the reaction occurring at low- and high-temperature regions. The reaction proceeds rapidly via a complex-mode mechanism below room temperature showing strong negative temperature dependence, where the effects of molecular attraction, H-atom tunneling and recrossing of collision complexes are found to be important. The temperature dependence of the rate constant between 400 and 1000 K is positive, the values increasing in accordance with the increase of the mean speed of collision. The rate constant varies from 7.6 Χ 10{sup -12} at 150 K to 3.7 Χ 10{sup -12} at 1000 K via a minimum value of 2.5 Χ 10{sup -12} cm{sup 3} molecule{sup -1} s{sup -1} at 400 K.

Effects of elevated ozone concentration on CH4 and N2O emission from paddy soil under fully open-air field conditions.

Science.gov (United States)

Tang, Haoye; Liu, Gang; Zhu, Jianguo; Kobayashi, Kazuhiko

2015-04-01

We investigated the effects of elevated ozone concentration (E-O3) on CH4 and N2O emission from paddies with two rice cultivars: an inbred Indica cultivar Yangdao 6 (YD6) and a hybrid one II-you 084 (IIY084), under fully open-air field conditions in China. A mean 26.7% enhancement of ozone concentration above the ambient level (A-O3) significantly reduced CH4 emission at tillering and flowering stages leading to a reduction of seasonal integral CH4 emission by 29.6% on average across the two cultivars. The reduced CH4 emission is associated with O3-induced reduction in the whole-plant biomass (-13.2%), root biomass (-34.7%), and maximum tiller number (-10.3%), all of which curbed the carbon supply for belowground CH4 production and its release from submerged soil to atmosphere. Although no significant difference was detected between the cultivars in the CH4 emission response to E-O3, a larger decrease in CH4 emission with IIY084 (-33.2%) than that with YD6 (-7.0%) was observed at tillering stage, which may be due to the larger reduction in tiller number in IIY084 by E-O3. Additionally, E-O3 reduced seasonal mean NOx flux by 5.7% and 11.8% with IIY084 and YD6, respectively, but the effects were not significant statistically. We found that the relative response of CH4 emission to E-O3 was not significantly different from those reported in open-top chamber experiments. This study has thus confirmed that increasing ozone concentration would mitigate the global warming potential of CH4 and suggested consideration of the feedback mechanism between ozone and its precursor emission into the projection of future ozone effects on terrestrial ecosystem. © 2014 John Wiley & Sons Ltd.

Synthesis of Fine Mo2C Powder from Prereduced Mo in Undiluted CH4 Flow

Science.gov (United States)

Cetinkaya, S.; Eroglu, S.

2017-10-01

The carburization behavior of prereduced Mo was investigated in undiluted CH4 flow at 900-1000 K. Prior to the experiments, equilibrium thermodynamic analysis was carried out in the Mo-C-H system. The products were characterized by mass measurement, x-ray diffraction and scanning electron microscopy techniques. A single Mo2C phase was obtained within 45 min, 5 min, and 2.5 min at 900 K, 950 K, and 1000 K, respectively, at CH4 contents higher than the predicted ones. The reasons for this behavior were discussed in terms of CH4 stability, open tube flow, and self-created atmosphere in the powder bed. The fractional conversion-time curves indicated that the carburization kinetics followed a linear rate law. The Mo2C crystallite size (26-37 nm) and platelet thickness (50-100 nm) were found to be smaller than those of the parent Mo phase. These findings were attributable to the defects formed as a result of stresses associated with the reduction and the carburization.

Thermodynamics of the production of condensed phases in the chemical vapor deposition of ZrC in the ZrCl{sub 4}–CH{sub 4}–H{sub 2}–Ar system

Energy Technology Data Exchange (ETDEWEB)

Liu, Haiping [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China); Deng, Juanli, E-mail: dengjl@chd.edu.cn [School of Materials Science and Engineering, Chang' an University, Xi' an, Shaanxi 710064 (China); Yang, Lianli [College of Chemistry and Chemical Engineering, Xianyang Teachers College, Xianyang, Shaanxi 712000 (China); Cheng, Laifei; Luo, Lei; Zhu, Yan [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China); Su, Kehe [Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China); Zhang, Litong [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China)

2014-05-02

Production conditions of ZrC, Zr and C(graphite) condensed phases in the chemical vapor deposition process with ZrCl{sub 4}–CH{sub 4}–H{sub 2}–Ar precursor system have been investigated based on thermodynamic analyses using the FactSage code. The yields of condensed phases have been examined as functions of the injected reactant ratios of ZrCl{sub 4}/(ZrCl{sub 4} + CH{sub 4}), H{sub 2}/(ZrCl{sub 4} + CH{sub 4}) and Ar/(ZrCl{sub 4} + CH{sub 4}), the temperature and the pressure. The results show that the yields strongly depend on the molar ratios of the ZrCl{sub 4}/(ZrCl{sub 4} + CH{sub 4}) and H{sub 2}/(ZrCl{sub 4} + CH{sub 4}) injected reactant and on the temperature, but are insensitive to the inert gas Ar ratio and pressure. The co-deposition of ZrC with Zr or C(graphite) can be easily controlled by changing the ratios of ZrCl{sub 4}/CH{sub 4} and H{sub 2}/(ZrCl{sub 4} + CH{sub 4}). Process conditions such as high input amount of H{sub 2}, relatively low amount of Ar, low pressure and temperature above 1300 K are favorable for the deposition of ZrC. The results of this work will be helpful for further experimental investigation on different deposition conditions. - Highlights: • Control of the composition of deposits via adjustment of precursor ratios • Carbon enrichment can be avoided using a low amount of argon diluting gas. • The deposition process is significantly influenced by the presence of hydrogen.

ELECTRON IRRADIATION OF KUIPER BELT SURFACE ICES: TERNARY N2-CH4-CO MIXTURES AS A CASE STUDY

International Nuclear Information System (INIS)

Kim, Y. S.; Kaiser, R. I.

2012-01-01

The space weathering of icy Kuiper Belt Objects was investigated in this case study by exposing methane (CH 4 ) and carbon monoxide (CO) doped nitrogen (N 2 ) ices at 10 K to ionizing radiation in the form of energetic electrons. Online and in situ Fourier transform infrared spectroscopy was utilized to monitor the radiation-induced chemical processing of these ices. Along with isocyanic acid (HNCO), the products could be mainly derived from those formed in irradiated binary ices of the N 2 -CH 4 and CO-CH 4 systems: nitrogen-bearing products were found in the form of hydrogen cyanide (HCN), hydrogen isocyanide (HNC), diazomethane (CH 2 N 2 ), and its radical fragment (HCN 2 ); oxygen-bearing products were of acetaldehyde (CH 3 CHO), formyl radical (HCO), and formaldehyde (H 2 CO). As in the pure ices, the methyl radical (CH 3 ) and ethane (C 2 H 6 ) were also detected, as were carbon dioxide (CO 2 ) and the azide radical (N 3 ). Based on the temporal evolution of the newly formed products, kinetic reaction schemes were then developed to fit the temporal profiles of the newly formed species, resulting in numerical sets of rate constants. The current study highlights important constraints on the preferential formation of isocyanic acid (HNCO) over hydrogen cyanide (HCN) and hydrogen isocyanide (HNC), thus guiding the astrobiological and chemical evolution of those distant bodies.

Methanogenic Conversion of CO2 Into CH4

Energy Technology Data Exchange (ETDEWEB)

Stevens, S.H., Ferry, J.G., Schoell, M.

2012-05-06

This SBIR project evaluated the potential to remediate geologic CO2 sequestration sites into useful methane gas fields by application of methanogenic bacteria. Such methanogens are present in a wide variety of natural environments, converting CO2 into CH4 under natural conditions. We conclude that the process is generally feasible to apply within many of the proposed CO2 storage reservoir settings. However, extensive further basic R&D still is needed to define the precise species, environments, nutrient growth accelerants, and economics of the methanogenic process. Consequently, the study team does not recommend Phase III commercial application of the technology at this early phase.

Photoelectron extraction efficiency from a CsI photocathode and THGEM operation in He−CF4 and He−CH4 mixtures

International Nuclear Information System (INIS)

Coimbra, A.E.C.; Santos, J.M.F. dos; Israelashvili, I.

2016-01-01

This work presents the experimental measurements obtained for UV-induced photo-electron extraction efficiency from a CsI photocathode into He with CF 4 and CH 4 gas mixtures. A 1000Å CsI photocathode was deposited on a gold plated THGEM for photo-electron conversion. Charge-gain measurements were obtained with a Single-THGEM detector operating in these gas mixtures using a continuous UV lamp for the extraction of photo-electrons. Charge-gains in excess of 10 5 were obtained for gas mixtures containing percentages of quencher higher than 20% while photo-electron extraction efficiency achieved ∼ 50% for He/CF 4 and ∼ 30% for He/CH 4 . Single photon electron measurements were also performed to assess the maximal gains reached in this regime. A discussion for future GPM cryogenic applications is presented

Formation and dissociation of CO{sub 2} and CO{sub 2}-THF hydrates compared to CH{sub 4} and CH{sub 4}-THF hydrates

Energy Technology Data Exchange (ETDEWEB)

Giavarini, C.; Maccioni, F.; Broggi, A. [Roma Univ. La Sapienza, Roma (Italy). Dept. of Chemical Engineering; Politi, M. [ENEL-RICERCHE, Brindisi (Italy)

2008-07-01

Carbon sequestration involves the removal of greenhouse gases from industrial or utility plant streams and their long term storage so that they cannot interact with the climate system. Different methods for selective carbon dioxide (CO{sub 2}) removal are in commercial use and are based on, gas absorption, membrane process, and cryogenic fractionation. In addition, disposal of captured CO{sub 2} in the ocean and in geological reservoirs has been proposed by researchers. Another challenge is to take advantage of the properties of CO{sub 2} hydrates for carbon sequestration since it could have a number of uses such as chemical production. As such, it is important to understand the hydrate decomposition kinetics during storage, transportation, and disposal. This paper presented a project that involved the separation of carbon dioxide from the flue gases of powers plants, in the form of hydrate. The project also involved the storage, use, and disposal of the hydrate. The purpose of the study was to evaluate the decomposition kinetics of CO{sub 2} hydrate containing different quantities of ice, at low pressures and temperatures between -3 and 0 degrees Celsius. In addition, in order to evaluate the tetrahydrofuran (THF) stabilization effect, the study examined the influence of THF on the formation and decomposition kinetics of mixed THF-methane (CH{sub 4}) and THF-CO{sub 2} hydrates. Preservation tests were conducted to determine the best pressure and temperature conditions for the mixed-hydrates conservation, with reference to the simple hydrates. The paper described the apparatus for the formation and dissociation tests which consisted of a jacketed stainless steel reactor, equipped with stirrer. The paper also described the hydrate formation procedure as well as hydrate characterization. Last, the paper discussed the hydrate dissociation tests that were conducted immediately after hydrate formation in the reactor. It was concluded that the hydrophilic and hydrophobic

Trajectory dynamics study of the Ar + CH4 dissociation reaction at high temperatures: the importance of zero-point-energy effects.

Science.gov (United States)

Marques, J M C; Martínez-Núñez, E; Fernandez-Ramos, A; Vazquez, S A

2005-06-23

Large-scale classical trajectory calculations have been performed to study the reaction Ar + CH4--> CH3 +H + Ar in the temperature range 2500 energy surface used for ArCH4 is the sum of the nonbonding pairwise potentials of Hase and collaborators (J. Chem. Phys. 2001, 114, 535) that models the intermolecular interaction and the CH4 intramolecular potential of Duchovic et al. (J. Phys. Chem. 1984, 88, 1339), which has been modified to account for the H-H repulsion at small bending angles. The thermal rate coefficient has been calculated, and the zero-point energy (ZPE) of the CH3 product molecule has been taken into account in the analysis of the results; also, two approaches have been applied for discarding predissociative trajectories. In both cases, good agreement is observed between the experimental and trajectory results after imposing the ZPE of CH3. The energy-transfer parameters have also been obtained from trajectory calculations and compared with available values estimated from experiment using the master equation formalism; in general, the agreement is good.

Impact of Equivalence Ratio on the Macrostructure of Premixed Swirling CH 4 /Air and CH 4 /O 2 /CO 2 Flames

KAUST Repository

Watanabe, Hirotatsu

2015-06-15

Premixed CH4/O2/CO2 flames (oxy-flames) and CH4/air flames (air-flames) were experimentally studied in a swirl-stabilized combustor. For comparing oxy and air flames, the same equivalence ratio and adiabatic flame temperature were used. CO2 dilution was adjusted to attain the same adiabatic temperature for the oxy-flame and the corresponding air-flame while keeping the equivalence ratio and Reynolds number (=20,000) the same. For high equivalence ratios, we observed flames stabilized along the inner and outer shear layers of the swirling flow and sudden expansion, respectively, in both flames. However, one notable difference between the two flames appears as the equivalence ratio reaches 0.60. At this point, the outer shear layer flame disappears in the air-flame while it persists in the oxy-flame, despite the lower burning velocity of the oxy-flame. Prior PIV measurements (Ref. 9) showed that the strains along the outer shear layer are higher than along the inner shear layer. Therefore, the extinction strain rates in both flames were calculated using a counter-flow premixed twin flame configuration. Calculations at the equivalence ratio of 0.60 show that the extinction strain rate is higher in the oxy than in the air flame, which help explain why it persists on the outer shear layer with higher strain rate. It is likely that extinction strain rates contribute to the oxy-flame stabilization when air flame extinguish in the outer shear layer. However, the trend reverses at higher equivalence ratio, and the cross point of the extinction strain rate appears at equivalence ratio of 0.64.

Precise soil management as a tool to reduce CH4 and N2O emissions from agricultural soils

NARCIS (Netherlands)

Mosquera Losada, J.; Hol, J.M.G.; Rappoldt, C.; Dolfing, J.

2007-01-01

Soil compaction stimulates the emission of nitrous oxide (N2O) and methane (CH4) from agricultural soils. N2O and CH4 are potent greenhouse gases, with a global warming potential respectively 296 times and 23 times greater than CO2.. Agricultural soils are an important source of N2O. Hence there is

Influence of O{sub 2} exposure on the interaction between CH{sub 4} and amorphous AlYB{sub 14}

Energy Technology Data Exchange (ETDEWEB)

Hunold, Oliver, E-mail: hunold@mch.rwth-aachen.de [Materials Chemistry, RWTH Aachen University, Kopernikusstr, 10, D-52074 Aachen (Germany); Wiesing, Martin; Arcos, Teresa de los [Technical and Macromolecular Chemistry, University of Paderborn, Warburger Str. 100, D-33098 Paderborn (Germany); Music, Denis [Materials Chemistry, RWTH Aachen University, Kopernikusstr, 10, D-52074 Aachen (Germany); Grundmeier, Guido [Technical and Macromolecular Chemistry, University of Paderborn, Warburger Str. 100, D-33098 Paderborn (Germany); Schneider, Jochen M. [Materials Chemistry, RWTH Aachen University, Kopernikusstr, 10, D-52074 Aachen (Germany)

2017-01-15

Highlights: • Influence of O{sub 2} exposure on the surface chemistry of a-AlYB{sub 14} on the interaction with CH{sub 4} and PE studied by ab initio and UHV-AFM. • Predicted stronger interaction is consistent with experimentally observed trends. • Upon O{sub 2} exposure surface bonding becomes more semiconducting causing a charge redistribution within the adsorbed CH{sub 4} molecule. • The data serve as proof of concept for exploring polymer − hard coating interactions in varying atmospheres. - Abstract: The influence of surface oxidation on the interaction between CH{sub 4} and amorphous AlYB{sub 14} (a-AlYB{sub 14}) has been studied theoretically by using density functional theory and experimentally by ultra-high vacuum atomic force microscopy (UHV-AFM). CH{sub 4} mimics the –CH{sub 3} termination and aliphatic subunits of a polymer chain. Low-energy ion scattering measurements of magnetron sputtered thin films suggest that the bonding at the surfaces of pristine a-AlYB{sub 14} and O{sub 2} exposed a-AlYB{sub 14} (O{sub 2}//a-AlYB{sub 14}) is metal-boron and metal-oxygen dominated, respectively. Based on the ab initio calculations the adsorption energies of CH{sub 4} on a-AlYB{sub 14} and O{sub 2}//a-AlYB{sub 14} decreases from −0.07 to −0.30 eV, respectively. This trend is consistent with experimental data obtained by colloidal probe UHV-AFM studies with a polyethylene sphere, where larger adhesion forces for the O{sub 2} exposed surface as compared to the pristine a-AlYB{sub 14} surface were measured. No charge transfer takes place between CH{sub 4} and the pristine as well as the O{sub 2} exposed a-AlYB{sub 14}. Oxygen chemisorption induces changes in surface bonding. States at the Fermi level are depleted upon oxidation, hence the surface bonding becomes more semiconducting causing a charge redistribution within the adsorbed CH{sub 4} molecule. Hence, these data serve as proof of concept for exploring the effect of O{sub 2} exposure on the

The global variation of CH4 and CO as seen by SCIAMACHY

NARCIS (Netherlands)

Straume, A.G.; Schrijver, H.; Gloudemans, A.M.S.; Houweling, S.; Aben, I.; Maurellis, A.N.; de Laat, A.T.J.; Kleipool, Q.; Lichtenberg, G.; van Hees, R.; Meirink, J.F.; Krol, M.

2005-01-01

The methane (CH4) and carbon monoxide (CO) total columns retrieved from SCIAMACHY's near-infrared channel 8 have been compared to satellite measurements by the MOPITT instrument and chemistry transport model calculations (TM3). Results from the SRON retrieval algorithm IMLM (v5.1) are presented here

Bio-refinery system of DME or CH4 production from black liquor gasification in pulp mills.

Science.gov (United States)

Naqvi, M; Yan, J; Fröling, M

2010-02-01

There is great interest in developing black liquor gasification technology over recent years for efficient recovery of bio-based residues in chemical pulp mills. Two potential technologies of producing dimethyl ether (DME) and methane (CH(4)) as alternative fuels from black liquor gasification integrated with the pulp mill have been studied and compared in this paper. System performance is evaluated based on: (i) comparison with the reference pulp mill, (ii) fuel to product efficiency (FTPE) and (iii) biofuel production potential (BPP). The comparison with the reference mill shows that black liquor to biofuel route will add a highly significant new revenue stream to the pulp industry. The results indicate a large potential of DME and CH(4) production globally in terms of black liquor availability. BPP and FTPE of CH(4) production is higher than DME due to more optimized integration with the pulping process and elimination of evaporation unit in the pulp mill.

Hydrogenation of organic matter as a terminal electron sink sustains high CO 2 :CH 4 production ratios during anaerobic decomposition

Energy Technology Data Exchange (ETDEWEB)

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.; Keller, Jason K.; Bridgham, Scott D.; Zalman, Cassandra Medvedeff; Meredith, Laura; Hanson, Paul J.; Hines, Mark; Pfeifer-Meister, Laurel; Saleska, Scott R.; Crill, Patrick; Cooper, William T.; Chanton, Jeff P.; Kostka, Joel E.

2017-10-01

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO2 and CH4 for each molecule of organic matter degraded. However, CO2:CH4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO2 has an oxidation state of +4, if CH4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO2:CH4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. This mechanism for CO2 generation without concomitant CH4 production has the potential to regulate the global warming potential of peatlands by elevating CO2:CH4 production ratios.

The predominance of young carbon in Arctic whole-lake CH4 and CO2 emissions and implications for Boreal yedoma lakes.

Science.gov (United States)

Elder, C.; Xu, X.; Walker, J. C.; Walter Anthony, K. M.; Pohlman, J.; Arp, C. D.; Townsend-Small, A.; Hinkel, K. M.; Czimczik, C. I.

2017-12-01

Lakes in Arctic and Boreal regions are hotspots for atmospheric exchange of the greenhouse gases CO2 and CH4. Thermokarst lakes are a subset of these Northern lakes that may further accelerate climate warming by mobilizing ancient permafrost C (> 11,500 years old) that has been disconnected from the active C cycle for millennia. Northern lakes are thus potentially powerful agents of the permafrost C-climate feedback. While they are critical for projecting the magnitude and timing these feedbacks from the rapidly warming circumpolar region, we lack datasets capturing the diversity of northern lakes, especially regarding their CH4contributions to whole-lake C emissions and their ability to access and mobilize ancient C. We measured the radiocarbon (14C) ages of CH4 and CO2 emitted from 60 understudied lakes and ponds in Arctic and Boreal Alaska during winter and summer to estimate the ages of the C sources yielding these gases. Integrated mean ages for whole-lake emissions were inferred from the 14C-age of dissolved gases sampled beneath seasonal ice. Additionally, we measured concentrations and 14C values of gases emitted by ebullition and diffusion in summer to apportion C emission pathways. Using a multi-sourced mass balance approach, we found that whole-lake CH4 and CO2 emissions were predominantly sourced from relatively young C in most lakes. In Arctic lakes, CH4 originated from 850 14C-year old C on average, whereas dissolved CO2 was sourced from 400 14C-year old C, and represented 99% of total dissolved C flux. Although ancient C had a minimal influence (11% of total emissions), we discovered that lakes in finer-textured aeolian deposits (Yedoma) emitted twice as much ancient C as lakes in sandy regions. In Boreal, yedoma-type lakes, CH4 and CO2 were fueled by significantly older sources, and mass balance results estimated CH4-ebullition to comprise 50-60% of whole-lake CH4 emissions. The mean 14C-age of Boreal emissions was 6,000 14C-years for CH4-C, and 2

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

Science.gov (United States)

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.

Greenhouse gas (CO2 and CH4) emissions from a high altitude hydroelectric reservoir in the tropics (Riogrande II, Colombia)

Science.gov (United States)

Guérin, Frédéric; Leon, Juan

2015-04-01

Tropical hydroelectric reservoirs are considered as very significant source of methane (CH4) and carbon dioxide (CO2), especially when flooding dense forest. We report emissions from the Rio Grande II Reservoir located at 2000 m.a.s.l. in the Colombian Andes. The dam was built at the confluence of the Rio Grande and Rio Chico in 1990. The reservoir has a surface of 12 km2, a maximum depth of 40m and a residence time of 2.5 month. Water quality (temperature, oxygen, pH, conductivity), nitrate, ammonium, dissolved and particulate organic carbon (DOC and POC), CO2 and CH4 were monitored bi-monthly during 1.5 year at 9 stations in the reservoir. Diffusive fluxes of CO2 and CH4 and CH4 ebullition were measured at 5 stations. The Rio grande II Reservoir is weakly stratified thermally with surface temperature ranging from 20 to 24°C and a constant bottom temperature of 18°C. The reservoir water column is well oxygenated at the surface and usually anoxic below 10m depth. At the stations close to the tributaries water inputs, the water column is well mixed and oxygenated from the surface to the bottom. As reported for other reservoirs located in "clear water" watersheds, the concentrations of nutrients are low (NO3-10 mmol m-2 d-1) were observed during the dry season. Close to the tributaries water inputs where the water column is well mixed, the average diffusive flux is 8 mmol m-2 d-1. CH4 ebullition was 3.5 mmol m-2 d-1 and no ebullition was observed for a water depth higher than 5m. The zone under the influence of the water inputs from tributaries represents 25% of the surface of the reservoir but contributed half of total CH4 emissions from the reservoir (29MgC month-1). Ebullition contributed only to 12% of total CH4 emissions over a year but it contributed up to 60% during the dry season. CH4 emissions from the Rio Grande Reservoir contributed 30% of the total GHG emissions (38GgCO2eq y-1). Overall, this study show that the majority of CH4 emissions from this

Exmination of catalytic reduction of NO by CH4 in a Pt-polybenimidazole membrane-Pt system with and without polarization

DEFF Research Database (Denmark)

Petrushina, Irina; Cleemann, Lars Nilausen; Bjerrum, Niels

“NO reduction in the NO, CH4, Ar/Pt/C//polybenzimidazole-H3PO4//Pt/C/H2, Ar was studied at 135°C”......“NO reduction in the NO, CH4, Ar/Pt/C//polybenzimidazole-H3PO4//Pt/C/H2, Ar was studied at 135°C”...

Near Infrared Cavity Ring-Down Spectroscopy for Isotopic Analyses of CH4 on Future Martian Surface Missions

Science.gov (United States)

Chen, Y.; Mahaffy P.; Holmes, V.; Burris, J.; Morey, P.; Lehmann, K.K.; Lollar, B. Sherwood; Lacrampe-Couloume, G.; Onstott, T.C.

2014-01-01

A compact Near Infrared Continuous Wave Cavity Ring-Down Spectrometer (near-IR-cw-CRDS) was developed as a candidate for future planetary surface missions. The optical cavity was made of titanium with rugged quartz windows to protect the delicate super cavity from the harsh environmental changes that it would experience during space flight and a Martian surface mission. This design assured the long-term stability of the system. The system applied three distributed feedback laser diodes (DFB-LD), two of which were tuned to the absorption line peaks of (sup 12)CH4 and (sup 13)CH4 at 6046.954 inverse centimeters and 6049.121 inverse centimeters, respectively. The third laser was tuned to a spectral-lines-free region for measuring the baseline cavity loss. The multiple laser design compensated for typical baseline drift of a CRDS system and, thus, improved the overall precision. A semiconductor optical amplifier (SOA) was used instead of an Acousto-Optic Module (AOM) to initiate the cavity ring-down events. It maintained high acquisition rates such as AOM, but consumed less power. High data acquisition rates combined with improved long-term stability yielded precise isotopic measurements in this near-IR region even though the strongest CH4 absorption line in this region is 140 times weaker than that of the strongest mid-IR absorption band. The current system has a detection limit of 1.4 times 10( sup –12) inverse centimeters for (sup 13)CH4. This limit corresponds to approximately 7 parts per trillion volume of CH4 at 100 Torrs. With no further improvements the detection limit of our current near IR-cw-CRDS at an ambient Martian pressure of approximately 6 Torrs (8 millibars) would be 0.25 parts per billion volume for one 3.3 minute long analysis.

Room temperature ferromagnetism and CH{sub 4} gas sensing of titanium oxynitride induced by milling and annealing

Energy Technology Data Exchange (ETDEWEB)

Bolokang, Amogelang S., E-mail: Sylvester.Bolokang@transnet.net [DST/CSIR National Centre for Nano-Structured Materials, Council for Scientific and Industrial Research, Pretoria, 0001 (South Africa); Transnet Engineering, Product Development, Private Bag X 528, Kilnerpark, 0127 (South Africa); Tshabalala, Zamaswazi P. [DST/CSIR National Centre for Nano-Structured Materials, Council for Scientific and Industrial Research, Pretoria, 0001 (South Africa); Malgas, Gerald F. [Department of Physics, University of the Western Cape, Private Bag X17, Bellville, 7535 (South Africa); Kortidis, Ioannis [DST/CSIR National Centre for Nano-Structured Materials, Council for Scientific and Industrial Research, Pretoria, 0001 (South Africa); West Virginia University, Department of Mechanical & Aerospace Engineering, Evansdale Campus, Morgantown, WV, 26506 (United States); Swart, Hendrik C. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein, ZA9300 (South Africa); Motaung, David E., E-mail: dmotaung@csir.co.za [DST/CSIR National Centre for Nano-Structured Materials, Council for Scientific and Industrial Research, Pretoria, 0001 (South Africa)

2017-06-01

We report on the room temperature ferromagnetism and CH{sub 4} gas sensing of titanium oxynitride prepared by milling and annealing at 1100 °C in a nitrogen gas environment. Structural analyses revealed a metastable orthorhombic TiO{sub 2} phase after milling for 120 h. The 120 h milled TiO{sub 2} particles and subsequently annealed in nitrogen gas at 1100 °C showed the formation of titanium oxynitride (TiO{sub x}N{sub y}) with a tetragonal crystal structure. An FCC metastable TiO{sub x}N{sub y} phase was also observed with a lattice parameter a = 4.235 Å. The vibrating sample magnetometer and electron paramagnetic analyses showed that the milled and TiO{sub x}N{sub y} samples possess room temperature ferromagnetism. Gas sensing measurements were carried out toward CH{sub 4} and H{sub 2} gases. The TiO{sub x}N{sub y} nanostructures demonstrated higher sensing response and selectivity to CH{sub 4} gas at room temperature. The enhanced response of 1010 and sensitivity of 50.12 ppm{sup -1} at a concentration of 20 ppm CH{sub 4} are associated with higher surface area, pore diameter and surface defects such as oxygen vacancies and Ti{sup 3+}, as evidenced from the Brunauer–Emmet–Teller, photoluminescence, electron paramagnetic resonance and x-ray photoelectron analyses. - Highlights: • Ball milled of TiO{sub 2} structure revealed metastable orthorhombic phase. • Upon nitridation tetragonal and FCC TiO{sub x}N{sub y} crystal structures were induced. • The magnetic properties of TiO{sub 2} nanoparticles was transformed by milling. • TiO{sub x}N{sub y} sensing response for CH{sub 4} gas at room temperature was high.

Optical sensor system for time-resolved quantification of methane densities in CH4-fueled spark ignition engines.

Science.gov (United States)

Golibrzuch, Kai; Digulla, Finn-Erik; Bauke, Stephan; Wackerbarth, Hainer; Thiele, Olaf; Berg, Thomas

2017-08-01

We present the development and the first application of an optical sensor system that allows single-cycle determination of methane (CH 4 ) concentration inside internal combustion (IC) engines. We use non-dispersive infrared absorption spectroscopy to detect the CH 4 density with a time resolution up to 33 μs at acquisition rates of 30 kHz. The measurement scheme takes advantage of the strong temperature dependence of the absorption band applying two detection channels for CH 4 that detect different spectral regions of the ν 3 anti-symmetric C-H-stretch absorption. The strategy allows the simultaneous determination of fuel concentration as well as gas temperature. We show the proof-of-concept by validation of the measurement strategy in static pressure cell experiments as well as its application to a methane-fueled IC engine using a modified spark plug probe. Our results clearly demonstrate that it is crucial to determine the CH 4 temperature in the probe volume. Due to thermal influences of the sensor probe, the temperature needed to calculate the desired quantities (fuel density, fuel concentration) significantly differs from the gas phase temperature in the rest of the combustion chamber and estimations from standard thermodynamic models, e.g., polytropic compression, will fail.

Tunable diode laser in-situ CH4 measurements aboard the CARIBIC passenger aircraft: instrument performance assessment

Science.gov (United States)

Dyroff, C.; Zahn, A.; Sanati, S.; Christner, E.; Rauthe-Schöch, A.; Schuck, T. J.

2014-03-01

A laser spectrometer for automated monthly measurements of methane (CH4) mixing ratios aboard the CARIBIC passenger aircraft is presented. The instrument is based on a commercial Fast Greenhouse Gas Analyser (FGGA, Los Gatos Res.), which was adapted to meet the requirements imposed by unattended airborne operation. It was characterised in the laboratory with respect to instrument stability, precision, cross sensitivity to H2O, and accuracy. For airborne operation, a calibration strategy is described that utilises CH4 measurements obtained from flask samples taken during the same flights. The precision of airborne measurements is 2 ppb for 10 s averages. The accuracy at aircraft cruising altitude is 3.85 ppb. During aircraft ascent and descent, where no flask samples were obtained, instrumental drifts can be less accurately determined and the uncertainty is estimated to be 12.4 ppb. A linear humidity bias correction was applied to the CH4 measurements, which was most important in the lower troposphere. On average, the correction bias was around 6.5 ppb at an altitude of 2 km, and negligible at cruising flight level. Observations from 103 long-distance flights are presented that span a large part of the northern hemispheric upper troposphere and lowermost stratosphere (UT/LMS), with occasional crossing of the tropics on flights to southern Africa. These accurate data mark the largest UT/LMS in-situ CH4 dataset worldwide. An example of a tracer-tracer correlation study with ozone is given, highlighting the possibility for accurate cross-tropopause transport analyses.