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.

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.

An automated GC-C-GC-IRMS setup to measure palaeoatmospheric δ13C-CH4, δ15N-N2O and δ18O-N2O in one ice core sample

Directory of Open Access Journals (Sweden)

P. Sperlich

2013-08-01

Full Text Available Air bubbles in ice core samples represent the only opportunity to study the mixing ratio and isotopic variability of palaeoatmospheric CH4 and N2O. The highest possible precision in isotope measurements is required to maximize the resolving power for CH4 and N2O sink and source reconstructions. We present a new setup to measure δ13C-CH4, δ15N-N2O and δ18O-N2O isotope ratios in one ice core sample and with one single IRMS instrument, with a precision of 0.09, 0.6 and 0.7‰, respectively, as determined on 0.6–1.6 nmol CH4 and 0.25–0.6 nmol N2O. The isotope ratios are referenced to the VPDB scale (δ13C-CH4, the N2-air scale (δ15N-N2O and the VSMOW scale (δ18O-N2O. Ice core samples of 200–500 g are melted while the air is constantly extracted to minimize gas dissolution. A helium carrier gas flow transports the sample through the analytical system. We introduce a new gold catalyst to oxidize CO to CO2 in the air sample. CH4 and N2O are then separated from N2, O2, Ar and CO2 before they get pre-concentrated and separated by gas chromatography. A combustion unit is required for δ13C-CH4 analysis, which is equipped with a constant oxygen supply as well as a post-combustion trap and a post-combustion GC column (GC-C-GC-IRMS. The post-combustion trap and the second GC column in the GC-C-GC-IRMS combination prevent Kr and N2O interferences during the isotopic analysis of CH4-derived CO2. These steps increase the time for δ13C-CH4 measurements, which is used to measure δ15N-N2O and δ18O-N2O first and then δ13C-CH4. The analytical time is adjusted to ensure stable conditions in the ion source before each sample gas enters the IRMS, thereby improving the precision achieved for measurements of CH4 and N2O on the same IRMS. The precision of our measurements is comparable to or better than that of recently published systems. Our setup is calibrated by analysing multiple reference gases that were injected over bubble-free ice samples. We show

Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH2CH3. Isolation of CH3CH2OC(O)SH

Science.gov (United States)

Juncal, Luciana C.; Cozzarín, Melina V.; Romano, Rosana M.

2015-03-01

ROC(S)SC(O)OCH2CH3, with R = CH3sbnd , (CH3)2CHsbnd and CH3(CH2)2sbnd , were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by 1H and 13C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R = CH3sbnd and (CH3)2CHsbnd , while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the Cdbnd S double bond anti (A) with respect to the Csbnd S single bond and the Ssbnd C single bond syn (S) with respect to the Cdbnd O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(Cdbnd O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(Cdbnd S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n → π∗ electronic transition associated with the Cdbnd S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.

Simulasi Numeris Karakteristik Pembakaran CH4/CO2/Udara dan CH4/CO2/O2 pada Counterflow Premixed Burner

Directory of Open Access Journals (Sweden)

Hangga Wicaksono

2017-08-01

Full Text Available The high amount of CO2 produced in a conventional biogas reactor needs to be considered. A further analysis is needed in order to investigate the effect of CO2 addition especially in thermal and chemical kinetics aspect. This numerical study has been held to analyze the effect of CO2 in CH4/CO2/O­2 and CH4/CO2/Air premixed combustion. In this study one dimensional analisys in a counterflow burner has been performed. The volume fraction of CO2 used in this study was 0%-40% from CH4’s volume fraction, according to the amount of CO2 in general phenomenon. Based on the flammability limits data, the volume fraction of CH4 used was 5-61% in O2 environment and 5-15% in air environment. The results showed a decreasing temperature along with the increasing percentage of CO2 in each mixtures, but the effect was quite smaller especially in stoichiometric and lean mixture. CO2 could affects thermally (by absorbing heat due to its high Cp and also made the production of unburnt fuel species such as CO relatively higher.

Optical emission spectroscopic study of Ar/H2/CH4 plasma during the production of graphene nano-flakes by induction plasma synthesis

International Nuclear Information System (INIS)

Mohanta, Antaryami; Lanfant, Briac; Asfaha, Mehari; Leparoux, Marc

2017-01-01

Graphene nano-flakes using CH 4 precursor were synthesized in a radio frequency inductively coupled plasma reactor with in-situ investigation of Ar/H 2 /CH 4 plasma by optical emission spectroscopy at fixed H 2 and Ar flow rates of 4 and 75 slpm, respectively, and at different plate powers (12 to 18 kW), pressures (400 to 700 mbar) and CH 4 flow rates (0.3 to 2 slpm). Emissions from C 2 Swan band, C 3 , CH and H 2 are observed in the optical emission spectra of Ar/H 2 /CH 4 plasma. Plasma temperature estimated analyzing the C 2 Swan band emission intensities is found to be decreased with increasing pressure and decreasing plate power. The decreasing plasma temperature gives rise to increase in production rate due to increase in condensation process. The production rate is observed to be increased from 0 to 0.3 g/h at 18 kW and from 0 to 1 g/h at 15 kW with increase in pressure from 400 to 700 mbar at fixed CH 4 flow rate of 0.7 slpm. Broad band continuum emission appears in the emission spectra at specific growth conditions in which the formation of vapor phase nanoparticles due to condensation of supersaturated vapor is facilitated. The production rate at 12 kW, 700 mbar, and 0.7 slpm of CH 4 flow rate is found to be 1.7 g/h which is more than that at 15 and 18 kW. Thus, the broadband continuum emission dominates the optical emission spectra at 12 kW due to lower temperature and higher production rate, and is attributed to the emission from suspended nanoparticles formed in vapor phase. The synthesized nanoparticles exhibit flake like structures having average length and width about 200 and 100 nm, respectively, irrespective of the growth conditions. Nano-flakes have thickness between 3.7 to 7.5 nm and are composed of 11 to 22 graphene layers depending on the growth conditions. The intensity ratio (I D /I G ) of D and G band observed in the Raman spectra is less than 0.33 which indicates good quality of the synthesized graphene nano-flakes. (paper)

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

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

Selective photocatalytic reduction of CO{sub 2} by H{sub 2}O/H{sub 2} to CH{sub 4} and CH{sub 3}OH over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalyst

Energy Technology Data Exchange (ETDEWEB)

Tahir, Muhammad, E-mail: mtahir@cheme.utm.my [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia); Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Punjab (Pakistan); Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia)

2016-12-15

Highlights: • Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalysts tested for CO{sub 2} photoreduction with H{sub 2}O/H{sub 2}. • Production of CH{sub 4} and CH{sub 3}OH depends on reductants type and metal-loading to TiO{sub 2}. • CH{sub 4} production over Cu-In/TiO{sub 2} was 1.5 fold more than In/TiO{sub 2} and 5 times the TiO{sub 2}. • The Cu-promoted CH{sub 3}OH production while In gave more CH{sub 4} with water vapors. • The H{sub 2} reductant gave negative effect for CH{sub 4} but enhanced CH{sub 3}OH production. - Abstract: Photocatalytic CO{sub 2} reduction by H{sub 2}O and/or H{sub 2} reductant to selective fuels over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N{sub 2} adsorption-desorption, UV–vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO{sub 2}, oxidized as Cu{sup 2+} and In{sup 3+}, promoted efficient separation of photo-generated electron/hole pairs (e{sup −}/h{sup +}). The results indicate that the reduction rate of CO{sub 2} by H{sub 2}O to CH{sub 4} approached to 181 μmol g{sup −1} h{sup −1} using 0.5% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst, a 1.53 fold higher than the production rate over the 3% In{sub 2}O{sub 3}/TiO{sub 2} and 5 times the amount produced over the pure TiO{sub 2}. In addition, Cu was found to promote efficient production of CH{sub 3}OH and yield rate reached to 68 μmol g{sup −1} h{sup −1} over 1% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H{sub 2} reductant was less favorable for CH{sub 4} production, yet a significant amount of CH{sub 4} and CH{sub 3}OH were obtained using a mixture of H{sub 2}O/H{sub 2} reductant. Therefore, Cu-loaded In{sub 2}O{sub 3}/TiO{sub 2} catalyst has shown to be capable for

The effect of CO2, H2O and SO2 on the kinetics of NO reduction by CH4 over La2O3

International Nuclear Information System (INIS)

Toops, Todd J.; Walters, Arden B.; Vannice, M.A.

2002-01-01

The effect of CO 2 , H 2 O and SO 2 on the kinetics of NO reduction by CH 4 over unsupported La 2 O 3 has been examined between 773 and 973K in the presence of O 2 in the feed. La 2 O 3 can maintain a stable, high specific activity (mol/(sm 2 )) for NO reduction with high concentrations of CO 2 and H 2 O in the feed; however, either of these two products reversibly inhibits the activity by about one-half in the presence of excess O 2 . The catalyst is poisoned by SO 2 at these temperatures and an oxysulfate phase is formed, but partial regeneration can be achieved at 1023K. CO 2 in the feed causes the formation of lanthanum oxycarbonate, which reverts to La 2 O 3 when CO 2 is removed, but no bulk La oxyhydroxide is detected after quenching with H 2 O in the feed. The influence of CO 2 and H 2 O on kinetic behavior can be described by assuming they compete with reactants for adsorption on surface sites, including them in the site balance equation, and using the rate expression proposed previously for NO reduction by CH 4 in excess O 2 . With O 2 in the feed, integral conversions of CH 4 and O 2 frequently occurred due to the direct combustion of CH 4 by O 2 , although NO conversions remained differential; thus, an integral reactor model was chosen to analyze the data which utilized a recently determined rate equation for CH 4 combustion on La 2 O 3 in conjunction with a previously proposed model for NO reduction by CH 4 . The following rate expression described the rate of N 2 formation: N 2 T = ' NO P NO P CH 4 P O 2 0.5 / 1 + K NO P NO + K CH 4 P CH 4 + K O 2 0.5 P O 2 0.5 + K CO 2 P CO 2 + K H 2 O P H 2 O 2 . It gave a good fit to the experimental rate data for NO reduction, as well as providing enthalpies and entropies of adsorption obtained from the fitting parameters that demonstrated thermodynamic consistency and were similar to previous values. The heats of adsorption were altered somewhat when either CO 2 or H 2 O was added to the feed, and the following

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.

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

Modeling Plasma-based CO2 and CH4 Conversion in Mixtures with N2, O2 and H2O: the Bigger Plasma Chemistry Picture

KAUST Repository

Wang, Weizong; Snoeckx, Ramses; Zhang, Xuming; Cha, Min; Bogaerts, Annemie

2018-01-01

performed regarding the single component gases, i.e. CO2 splitting and CH4 reforming, as well as for two component mixtures, i.e. dry reforming of methane (CO2/CH4), partial oxidation of methane (CH4/O2), artificial photosynthesis (CO2/H2O), CO2

Evaluation of factors affecting accurate measurements of atmospheric CO2 and CH4 by wavelength-scanned cavity ring-down spectroscopy

Science.gov (United States)

Nara, H.; Tanimoto, H.; Tohjima, Y.; Mukai, H.; Nojiri, Y.; Katsumata, K.; Rella, C.

2012-07-01

We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Variations in the composition of the background gas substantially impacted the CO2 and CH4 measurements: the measured amounts of CO2 and CH4 decreased with increasing N2 mole fraction, but increased with increasing O2 and Ar, suggesting that the pressure-broadening effects (PBEs) increased as Ar < O2 < N2. Using these experimental results, we inferred PBEs for the measurement of synthetic standard gases. The PBEs were negligible (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) for gas standards balanced with purified air, although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived empirical correction functions for water vapor for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301). Although the transferability of the functions was not clear, no significant difference was found in the water vapor correction values among these instruments within the typical analytical precision at sufficiently low water concentrations (< 0.3%V for CO2 and < 0.4%V for CH4). For accurate measurements of CO2 and CH4 in ambient air, we concluded that WS-CRDS measurements should be performed under complete dehumidification of air samples, or moderate dehumidification followed by application of a water vapor correction function, along with calibration by natural air-based standard gases or purified air-balanced synthetic standard gases with isotopic correction.

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.

Modeling Plasma-based CO2 and CH4 Conversion in Mixtures with N2, O2 and H2O: the Bigger Plasma Chemistry Picture

KAUST Repository

Wang, Weizong

2018-01-18

Due to the unique properties of plasma technology, its use in gas conversion applications is gaining significant interest around the globe. Plasma-based CO2 and CH4 conversion have become major research areas. Many investigations have already been performed regarding the single component gases, i.e. CO2 splitting and CH4 reforming, as well as for two component mixtures, i.e. dry reforming of methane (CO2/CH4), partial oxidation of methane (CH4/O2), artificial photosynthesis (CO2/H2O), CO2 hydrogenation (CO2/H2), and even first steps towards the influence of N2 impurities have been taken, i.e. CO2/N2 and CH4/N2. In this feature article we briefly discuss the advances made in literature for these different steps from a plasma chemistry modeling point of view. Subsequently, we present a comprehensive plasma chemistry set, combining the knowledge gathered in this field so far, and supported with extensive experimental data. This set can be used for chemical kinetics plasma modeling for all possible combinations of CO2, CH4, N2, O2 and H2O, to investigate the bigger picture of the underlying plasmachemical pathways for these mixtures in a dielectric barrier discharge plasma. This is extremely valuable for the optimization of existing plasma-based CO2 conversion and CH4 reforming processes, as well as for investigating the influence of N2, O2 and H2O on these processes, and even to support plasma-based multi-reforming processes.

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...

High temperature infrared absorption cross sections of methane near 3.4 μm in Ar and CO2 mixtures

Science.gov (United States)

Koroglu, Batikan; Neupane, Sneha; Pryor, Owen; Peale, Robert E.; Vasu, Subith S.

2018-02-01

The absorption cross-sections of CH4 at two wavelengths in the mid-IR region: λpeak = 3403.4 nm and λvalley = 3403.7 nm were measured. Data were taken using three different compositions of non-reactive gas mixtures comprising CH4/Ar/CO2 between 700 laser. Also, broadband room temperature methane cross section measurements were performed using a Fourier transform infrared spectrometer and the cascade laser to gain a better insight into the changes of the line shapes in various bath gasses (Ar, CO2, and N2). An application of the high-temperature cross-section data was demonstrated to determine the concentration of methane during oxy-methane combustion in a mixture of CO2, O2, and Ar. Current measurements will be valuable addition to the spectroscopy database for methane- an important fuel used for power generation and heating around the world.

A chiral mixed carboxylate, [Nd4(H2O)2(OOC(CH2)3COO)4(C2O4)2], exhibiting NLO properties

International Nuclear Information System (INIS)

Vaidhyanathan, R.; Natarajan, Srinivasan; Rao, C.N.R.

2004-01-01

Reaction of a mixture of neodymium carbonate, HCl, oxamic acid and glutaric acid under hydrothermal conditions gives rise to a new mixed carboxylate of neodymium, [Nd 4 (H 2 O) 2 (OOC(CH 2 ) 3 COO) 4 (C 2 O 4 ) 2 ], I. The structure, determined using single crystal X-ray diffraction, comprises a helical column formed by the grafting of the oxalate unit on to helical NdO 9 chains, cross-linked by the glutarate anions. It is noteworthy that the pitch of the helix is equivalent to the length of the oxalate unit. Furthermore, I shows about 1.1 times the SHG activity of urea

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.

Influence of the pressure and power on the non-equilibrium plasma chemistry of C{sub 2}, C{sub 2}H, C{sub 2}H{sub 2}, CH{sub 3} and CH{sub 4} affecting the synthesis of nanodiamond thin films from C{sub 2}H{sub 2} (1%)/H{sub 2}/Ar-rich plasmas

Energy Technology Data Exchange (ETDEWEB)

Gordillo-Vazquez, F J [Instituto de Optica, C.S.I.C., Serrano 121, 28006 Madrid (Spain); Albella, J M [Instituto de Materiales de Madrid, C.S.I.C., Cantoblanco, 28049 Madrid (Spain)

2004-02-01

We have used a kinetic model to investigate the influence of changing the pressure (0.1-0.8 Torr) and power (100-300 W) on the non-equilibrium plasma chemistry of RF (13.56 MHz) produced C{sub 2}H{sub 2} (1%)/H{sub 2}/Ar plasmas of interest for the synthesis of nanodiamond thin films. We found that the concentrations of the species C{sub 2}(X{sup 1}SIGMA{sup +}{sub g}), C{sub 2}(a{sup 3}PI{sub u}) and C{sub 2}H are not sensitive to variations in the power but they exhibit a significant increase when the pressure decreases at high argon content in the plasma. In addition, the concentrations of C{sub 2}H{sub 2}, CH{sub 4} and CH{sub 3} exhibit a slight (case of C{sub 2}H{sub 2}) or negligible (case of CH{sub 3} and CH{sub 4}) power-dependence although they decrease (case of C{sub 2}H{sub 2} and CH{sub 4}) or remain almost constant (case of CH{sub 3}) as the pressure decreases. A reasonable agreement is found when comparing the model predictions with available experimental results. These findings provide a basic understanding of the plasma chemistry of hydrocarbon/Ar-rich plasma environments and, at the same time, can be of interest to optimize the processing conditions of nanodiamond films from medium pressure RF hydrocarbon/Ar-rich plasmas.

Air-Sea Interactions of Natural Long-Lived Greenhouse Gases (CO2, N2O, CH4) in a Changing Climate

Digital Repository Service at National Institute of Oceanography (India)

Bakker, D.C.E.; Bange, H.W.; Gruber, N.; Johannessen, T.; Upstill-Goddard, R.C.; Borges, A.V.; Delille, B.; Loscher, C.R.; Naqvi, S.W.A.; Omar, A.M.; Santana-Casiano, J.M.

at m o sp h er ic li fe ti m es G as R o le in at m o sp h er ic ch em is tr y O ce an ic co n tr ib u ti o n to co n te m p o ra ry at m o sp h er ic b u d g et Im p ac t o f en v ir o n m en ta l ch an g e o n ai r- se a g as ex ch an g e in th e tw... en ty -fi rs t ce n tu ry G lo b al w ar m in g O ce an ac id ifi ca ti o n O p en o ce an d eo x y g en at io n C o as ta l eu tr o p h ic at io n an d h y p o x ia C O 2 In er t N et o ce an si n k fo r ab o u t 3 0 % o f C O 2 em is si o n s fr o m...

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

Investigating cluster formation in adsorption of CO2, CH4, and Ar in zeolites and metal organic frameworks at subcritical temperatures

NARCIS (Netherlands)

Krishna, R.; van Baten, J.M.

2010-01-01

The critical temperatures, T-c, of CO2, CH4, and Ar are 304 K, 191 K, and 151 K, respectively. This paper highlights some unusual characteristics of adsorption and diffusion of these molecules in microporous structures such as zeolites and metal organic frameworks at temperatures T < T-c. Published

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

Mechanistic Study of Ni/CeO{sub 2}-catalyzed CO{sub 2}/CH{sub 4} Reaction Using Flow and Static Methods

Energy Technology Data Exchange (ETDEWEB)

Kang, Jin-Gyu; Roh, Joong-Seok; Kim, Ji-Yeong; Lee, Sung-Han; Choi, Jonng-Gill [Yonsei University, Seoul (Korea, Republic of)

2016-08-15

Ni/CeO{sub 2} catalysts with different Ni loadings (5, 7, 10, 12, and 14 wt% Ni) were prepared by an impregnation method and examined for the CO{sub 2} reforming of methane using flow and static reactors. Their catalytic activities and selectivities were measured under CO{sub 2}/CH{sub 4}/Ar (=5/5/40 cm{sup 3}/min) flow at 450-800 .deg. C using a flow reactor system with an on-line gas chromatography. At flexed temperature, the CO{sub 2} and CH{sub 4} conversions varied only slightly with the Ni wt%, whereas the H{sub 2}/CO ratio increased with increasing Ni wt%. The conversions increased with temperature, reaching 98% at 800 .deg. C. The H{sub 2}/CO ratio varied with temperature in the range of 450-800 .deg. C, from less than 1 below 550 .deg. C to close to 1 at 550-600 .deg. C and then back to less than 1 above 600 .deg. C. The apparent activation energies were determined to be 43.1 kJ/mol for the CO{sub 2} consumption and 50.2 kJ/mol for the CH{sub 4} consumption based on the rates measured for the reforming reaction over 5 wt% Ni/CeO{sub 2} catalyst at 550-750 .deg. C. Additionally, the catalytic reforming reaction at low pressure (40 Torr) was investigated by a static reactor system by using a differential photoacoustic cell, in which the rates were measured from the CO{sub 2} photoacoustic signal data at early reaction times over the temperature range of 460-610 .deg. C. Apparent activation energies of 25.5-30.1 kJ/mol were calculated from the CO{sub 2} disappearance rates. The CO{sub 2} adsorption on the Ni/CeO{sub 2} catalyst was investigated by the CO{sub 2} photoacoustic spectroscopy and Fourier transform infrared spectroscopy. Feasible side reactions during the catalytic CO{sub 2}/CH{sub 4} reaction were suggested on the basis of the kinetic and spectroscopic results.

SOLAR-WIND ION-DRIVEN X-RAY EMISSION FROM COMETARY AND PLANETARY ATMOSPHERES: MEASUREMENTS AND THEORETICAL PREDICTIONS OF CHARGE-EXCHANGE CROSS-SECTIONS AND EMISSION SPECTRA FOR O{sup 6+} + H{sub 2}O, CO, CO{sub 2}, CH{sub 4}, N{sub 2}, NO, N{sub 2}O, AND Ar

Energy Technology Data Exchange (ETDEWEB)

Machacek, J. R. [Atomic and Molecular Physics Laboratory, Research School of Physics and Engineering, The Australian National University, Canberra 2601 (Australia); Mahapatra, D. P. [Department of Physics, Utkal University, Bhubaneswar 751004 (India); Schultz, D. R. [Department of Physics, Univ. of North Texas, Denton, TX 76203 (United States); Ralchenko, Yu. [Atomic Spectroscopy Group, National Institute of Standards and Technology, Gaithersburg, MD 20899-8422 (United States); Moradmand, A.; El Ghazaly, M. O. A.; Chutjian, A. [Astrophysics and Space Sciences Section, Jet Propulsion Laboratory/Caltech, Pasadena, CA 91109 (United States)

2015-08-10

Relevant to modeling and understanding X-ray emission from cometary and planetary atmospheres, total cross-sections for 1.17 and 2.33 keV/u O{sup 6+} colliding with H{sub 2}O, CO, CO{sub 2}, CH{sub 4}, N{sub 2}, NO, N{sub 2}O, and Ar have been measured for the processes of single, double, and triple charge exchanges. Using these measurements as benchmarks, synthetic emission spectra spanning the X-ray, UV, and visible range have been calculated based on theoretical treatment of the transfer of between one and six electrons from the target neutrals to the projectile ion, followed by radiative and non-radiative decay of the highly excited states produced in these collisions. The results help add to the base of knowledge required to simulate ion-neutral processes in astrophysical environments; refine the present understanding of these fundamental atomic processes; and guide future observations, laboratory measurements, and theoretical predictions.

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.

Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis.

Science.gov (United States)

Uruş, Serhan

2016-12-15

The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Profiles of CH4, HDO, H2O, and N2O with improved lower tropospheric vertical resolution from Aura TES radiances

Directory of Open Access Journals (Sweden)

D. Noone

2012-02-01

Full Text Available Thermal infrared (IR radiances measured near 8 microns contain information about the vertical distribution of water vapor (H2O, the water isotopologue HDO, and methane (CH4, key gases in the water and carbon cycles. Previous versions (Version 4 or less of the TES profile retrieval algorithm used a "spectral-window" approach to minimize uncertainty from interfering species at the expense of reduced vertical resolution and sensitivity. In this manuscript we document changes to the vertical resolution and uncertainties of the TES version 5 retrieval algorithm. In this version (Version 5, joint estimates of H2O, HDO, CH4 and nitrous oxide (N2O are made using radiances from almost the entire spectral region between 1100 cm−1 and 1330 cm−1. The TES retrieval constraints are also modified in order to better use this information. The new H2O estimates show improved vertical resolution in the lower troposphere and boundary layer, while the new HDO/H2O estimates can now profile the HDO/H2O ratio between 925 hPa and 450 hPa in the tropics and during summertime at high latitudes. The new retrievals are now sensitive to methane in the free troposphere between 800 and 150 mb with peak sensitivity near 500 hPa; whereas in previous versions the sensitivity peaked at 200 hPa. However, the upper troposphere methane concentrations are biased high relative to the lower troposphere by approximately 4% on average. This bias is likely related to temperature, calibration, and/or methane spectroscopy errors. This bias can be mitigated by normalizing the CH4 estimate by the ratio of the N2O estimate relative to the N2O prior, under the assumption that the same systematic error affects both the N2O and CH4 estimates. We demonstrate that applying this ratio theoretically reduces the CH4 estimate for non-retrieved parameters that jointly affect both the N2O and CH4 estimates. The relative upper troposphere to lower troposphere bias is approximately 2.8% after this bias

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.

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO{sub 2}(CH{sub 3}SO{sub 3}){sub 2}, UO{sub 2}(CH{sub 3}SO{sub 3}){sub 2}, ReO{sub 3}(CH{sub 3}SO{sub 3}), VO(CH{sub 3}SO{sub 3}){sub 2}, and V{sub 2}O{sub 3}(CH{sub 3}SO{sub 3}){sub 4} and their thermal decomposition under N{sub 2} and O{sub 2} atmosphere

Energy Technology Data Exchange (ETDEWEB)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S. [Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry (Germany)

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO{sub 3}, UO{sub 2}(CH{sub 3}COO){sub 2}.2 H{sub 2}O, Re{sub 2}O{sub 7}(H{sub 2}O){sub 2}, and V{sub 2}O{sub 5} with CH{sub 3}SO{sub 3}H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO{sub 2}(CH{sub 3}SO{sub 3}){sub 2} (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm{sup 3}, Z=8) contains [MoO{sub 2}] moieties connected by [CH{sub 3}SO{sub 3}] ions to form layers parallel to (100). UO{sub 2}(CH{sub 3}SO{sub 3}){sub 2} (P2{sub 1}/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) {sup circle}, V=1.8937(3) nm{sup 3}, Z=8) consists of linear UO{sub 2}{sup 2+} ions coordinated by five [CH{sub 3}SO{sub 3}] ions, forming a layer structure. VO(CH{sub 3}SO{sub 3}){sub 2} (P2{sub 1}/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) {sup circle}, V=0.8290(2) nm{sup 3}, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO{sub 3}(CH{sub 3}SO{sub 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) {sup circle}, V=1.1523(4) nm{sup 3}, Z=8) a chain structure exhibiting infinite O-[ReO{sub 2}]-O-[ReO{sub 2}]-O chains is formed. Each [ReO{sub 2}]-O-[ReO{sub 2}] unit is coordinated by two bidentate [CH{sub 3}SO{sub 3}] ions. V{sub 2}O{sub 3}(CH{sub 3}SO{sub 3}){sub 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{sup 3}, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH{sub 3}SO{sub 3}] ligands. Additional methanesulfonate ions connect the [V{sub 2}O{sub 3}] groups along [001]. Thermal decomposition of the compounds was monitored under N{sub 2} and O{sub 2} atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N{sub 2} the decomposition proceeds

The ChArMEx database

Science.gov (United States)

Ferré, Hélène; Belmahfoud, Nizar; Boichard, Jean-Luc; Brissebrat, Guillaume; Cloché, Sophie; Descloitres, Jacques; Fleury, Laurence; Focsa, Loredana; Henriot, Nicolas; Mière, Arnaud; Ramage, Karim; Vermeulen, Anne; Boulanger, Damien

2015-04-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr/) aims at a scientific assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The project includes long term monitoring of environmental parameters , intensive field campaigns, use of satellite data and modelling studies. Therefore ChARMEx scientists produce and need to access a wide diversity of data. In this context, the objective of the database task is to organize data management, distribution system and services, such as facilitating the exchange of information and stimulating the collaboration between researchers within the ChArMEx community, and beyond. The database relies on a strong collaboration between ICARE, IPSL and OMP data centers and has been set up in the framework of the Mediterranean Integrated Studies at Regional And Locals Scales (MISTRALS) program data portal. ChArMEx data, either produced or used by the project, are documented and accessible through the database website: http://mistrals.sedoo.fr/ChArMEx. The website offers the usual but user-friendly functionalities: data catalog, user registration procedure, search tool to select and access data... The metadata (data description) are standardized, and comply with international standards (ISO 19115-19139; INSPIRE European Directive; Global Change Master Directory Thesaurus). A Digital Object Identifier (DOI) assignement procedure allows to automatically register the datasets, in order to make them easier to access, cite, reuse and verify. At present, the ChArMEx database contains about 120 datasets, including more than 80 in situ datasets (2012, 2013 and 2014 summer campaigns, background monitoring station of Ersa...), 25 model output sets (dust model intercomparison, MEDCORDEX scenarios...), a high resolution emission inventory over the Mediterranean... Many in situ datasets

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.

Hydrogen constituents of the mesosphere inferred from positive ions - H2O, CH4, H2CO, H2O2, and HCN

Science.gov (United States)

Kopp, E.

1990-01-01

The concentrations in the mesosphere of H2O, CH4, H2CO, H2O2, and HCN were inferred from data on positive ion compositions, obtained from one mid-latitude and four high-latitude rocket flights. The inferred concentrations were found to agree only partially with the ground-based microwave measurements and/or model prediction by Garcia and Solomon (1985). The CH4 concentration was found to vary between 70 and 4 ppb in daytime and 900 and 100 ppbv at night, respectively. Unexpectedly high H2CO concentrations were obtained, with H2CO/H2O ratios between 0.0006 and 0.1, and a mean HCN volume mixing ratio of 6 x 10 to the -10th was inferred.

Action mechanism of hydrogen gas on deposition of HfC coating using HfCl{sub 4}-CH{sub 4}-H{sub 2}-Ar system

Energy Technology Data Exchange (ETDEWEB)

Wang, Yalei, E-mail: yaleipm@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); School of Metallurgy and Environment, Central South University, Changsha, 410083 (China); Li, Zehao [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); Xiong, Xiang, E-mail: xiongx@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); Li, Xiaobin [School of Metallurgy and Environment, Central South University, Changsha, 410083 (China); Chen, Zhaoke; Sun, Wei [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China)

2016-12-30

Highlights: • HfC coatings were deposited on C/C composites by LPCVD using HfCl4-CH4-H2-Ar system. • Action mechanism of H2 on structure and growth behavior of HfC coating was studied. • Increased H2 concentration leads to transformation in growth mechanism of coating. - Abstract: Hafnium carbide coatings were deposited on carbon/carbon composites by low pressure chemical vapor deposition using HfCl{sub 4}-CH{sub 4}-H{sub 2}-Ar system. The microstructure, mechanical and ablation resistance performance of HfC coatings deposited with various H{sub 2} concentrations were investigated. The effect of hydrogen gas on the deposition of HfC coating was also discussed. Results show that all of the deposited coatings are composed of single cubic HfC phase, the hydrogen gas acted as a crucial role in determining the preferred orientation, microstructure and growth behavior of HfC coatings. During the deposition process, the gas phase supersaturation of the reaction species can be controlled by adjusting the hydrogen gas concentration. When deposited with low hydrogen gas concentration, the coating growth was dominated by the nucleation of HfC, which results in the particle-stacked structure of HfC coating. Otherwise, the coating growth was dominated by the crystal growth at high hydrogen gas concentration, which leads to the column-arranged structure of HfC coating. Under the ablation environment, the coating C2 exhibits better configurational stability and ablation resistance. The coating structure has a significant influence on the mechanical and ablation resistance properties of HfC coating.

Enhanced photocatalytic CO2 reduction to CH4 over separated dual co-catalysts Au and RuO2

Science.gov (United States)

Dong, Chunyang; Hu, Songchang; Xing, Mingyang; Zhang, Jinlong

2018-04-01

A spatially separated, dual co-catalyst photocatalytic system was constructed by the stepwise introduction of RuO2 and Au nanoparticles (NPs) at the internal and external surfaces of a three dimensional, hierarchically ordered TiO2-SiO2 (HTSO) framework (the final photocatalyst was denoted as Au/HRTSO). Characterization by HR-TEM, EDS-mapping, XRD and XPS confirmed the existence and spatially separated locations of Au and RuO2. In CO2 photocatalytic reduction (CO2PR), Au/HRTSO (0.8%) shows the optimal performance in both the activity and selectivity towards CH4; the CH4 yield is almost twice that of the singular Au/HTSO or HRTSO (0.8%, weight percentage of RuO2) counterparts. Generally, Au NPs at the external surface act as electron trapping agents and RuO2 NPs at the inner surface act as hole collectors. This advanced spatial configuration could promote charge separation and transfer efficiency, leading to enhanced CO2PR performance in both the yield and selectivity toward CH4 under simulated solar light irradiation.

Potential hydroxyl ultraviolet laser. [Ar-H/sub 2/O

Energy Technology Data Exchange (ETDEWEB)

Chen, C H; Payne, M G

1976-09-01

A strong emission band extending from 3060 to 3120 A was observed following proton beam excitation of an Ar--H/sub 2/O mixture. This emission band was assigned to the transition of OH(A/sup 2/Sigma/sup +/)/sub nu=o/ ..-->.. OH(X/sup 2/Pi)/sub nu=o/. At high argon partial pressure (> 200 torr), the precursor of this emission band is believed to be the argon excimer Ar/sup *//sub 2/(1/sub u/). The fluorescence efficiency of Ar--H/sub 2/O is estimated to be a factor of 4 times that of Ar--N/sub 2/. Development of a highly efficient, tunable uv laser by e-beam pumping is promising.

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

Atmospheric chemistry of C₄F₉O(CH₂)₃OC₄F₉ and CF₃CFHCF₂O (CH₂)₃OCF₃CFHCF₂

DEFF Research Database (Denmark)

Toft, A. M.; Hurley, M. D.; Wallington, T. J.

2006-01-01

FTIR smog chamber techniques were used to measure k(Cl + CF3CFHCF2O(CH2)(3)OCF2CFHCF3) = (2.97 +/- 0.17) x 10(-12) k(OH + CF3CFHCF2O(CH2)(3)OCF2CFHCF3) = (2.45 +/- 0.14) x 10(-13), k(Cl + C4F9O(CH2)(3)OC4F9) = (1.45 +/- 0.16) x 10(-12), and k(OH + C4F9O(CH2)(3)OC4F9) = (1.44 +/- 0.10) x 10(-13) c...

A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

Science.gov (United States)

Watson, R.; Machado, G.; Fischer, S.; Davis, D. D.

1976-01-01

The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

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.

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.

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.

The use of CO 2 as an additive for ignition delay and pollutant control in CH 4 /air autoignition

KAUST Repository

Tingas, Efstathios Al.

2017-10-05

The effect of CO2 dilution on the adiabatic and isochoric autoignition of CH4/air mixtures is analyzed with Computational Singular Perturbation (CSP) algorithmic tools, with a particular emphasis on the determination of the features of the chemical dynamics that control ignition delay and emission formation. Increasing CO2 dilution causes longer ignition delays, lower final temperatures and decreased formation of NO and CO. These effects of CO2 dilution are shown to be entirely thermal, contrary to what happens with dilution with H2O, which also has chemical activity and can reduce ignition delay. For the same initial mole fraction of the diluent, the decrease in final temperature and in NO concentration is larger in the CO2 case whereas the decrease in CO is larger in the H2O case. The thermal effect of CO2 is entirely analogous with those of dilution with the chemically inert Ar, only stronger for the same percentage of initial dilution, because of the larger specific heat of CO2. The reactions that have the largest contribution to the characteristic explosive time scale of the system during ignition delay (H2O2(+M)→OH+OH(+M), CH3O2+CH2O→CH3O2H+HCO, CH4+CH3O2→CH3+CH3O2H, H+O2→O+OH, etc.) are not substantially affected by CO2 dilution, neither are the species that are pointed by CSP (CH3O2, H2O2, CH2O, etc.) as having the largest impact on the this timescale. The same holds for the modes that control CO and NO formation. The results point to the possibility of cold exhaust gas recirculation being used in order to produce mixtures with longer ignition delays and therefore substantial resistance to uncontrolled ignition.

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...

The ChArMEx database

Science.gov (United States)

Ferré, Hélène; Descloitres, Jacques; Fleury, Laurence; Boichard, Jean-Luc; Brissebrat, Guillaume; Focsa, Loredana; Henriot, Nicolas; Mastrorillo, Laurence; Mière, Arnaud; Vermeulen, Anne

2013-04-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr/) aims at a scientific assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The project includes long term monitoring of environmental parameters, intensive field campaigns, use of satellite data and modelling studies. Therefore ChARMEx scientists produce and need to access a wide diversity of data. In this context, the objective of the database task is to organize data management, distribution system and services such as facilitating the exchange of information and stimulating the collaboration between researchers within the ChArMEx community, and beyond. The database relies on a strong collaboration between OMP and ICARE data centres and falls within the scope of the Mediterranean Integrated Studies at Regional And Locals Scales (MISTRALS) program data portal. All the data produced by or of interest for the ChArMEx community will be documented in the data catalogue and accessible through the database website: http://mistrals.sedoo.fr/ChArMEx. The database website offers different tools: - A registration procedure which enables any scientist to accept the data policy and apply for a user database account. - Forms to document observations or products that will be provided to the database in compliance with metadata international standards (ISO 19115-19139; INSPIRE; Global Change Master Directory Thesaurus). - A search tool to browse the catalogue using thematic, geographic and/or temporal criteria. - Sorted lists of the datasets by thematic keywords, by measured parameters, by instruments or by platform type. - A shopping-cart web interface to order in situ data files. At present datasets from the background monitoring station of Ersa, Cape Corsica and from the 2012 ChArMEx pre-campaign are available. - A user-friendly access to satellite products

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

Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

KAUST Repository

Chen, Yin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Emsley, Lyndon; Basset, Jean-Marie

2015-01-01

By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

KAUST Repository

Chen, Yin

2015-01-21

By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

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.

[H3N(CH2)4NH3]2[Al4(C2O4)(H2PO4)2(PO4)4].4[H2O]: A new layered aluminum phosphate-oxalate

International Nuclear Information System (INIS)

Peng Li; Li Jiyang; Yu Jihong; Li Guanghua; Fang Qianrong; Xu Ruren

2005-01-01

A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H 3 N(CH 2 ) 4 NH 3 ] 2 [Al 4 (C 2 O 4 )(H 2 PO 4 ) 2 (PO 4 ) 4 ].4[H 2 O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, 31 P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) A, b=8.8608(8) A, c=13.2224(11) A, α=80.830(6) deg. , β=74.965(5) deg. , γ=78.782(6) deg. , Z=2, R 1[ I >2 σ ( I )] =0.0511 and wR 2(alldata) =0.1423. The alternation of AlO 4 tetrahedra and PO 4 tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO 6 octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO 6 , and bridging the adjacent AlO 6 octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions. -- Graphical abstract: The alternation of AlO 4 tetrahedra and PO 4 tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO 6 octahedra to form the layered structure with 4,6-net sheet. Oxalate ions are bis-bidentately boned by participating in the coordination of AlO 6 , and bridging the adjacent AlO 6 octahedra

Development and characterization of polyethersulfone/TiO2 mixed matrix membranes for CO2/CH4 separation

Science.gov (United States)

Galaleldin, S.; Mannan, H. A.; Mukhtar, H.

2017-12-01

In this study, mixed matrix membranes comprised of polyethersulfone as the bulk polymer phase and titanium dioxide (TiO2) nanoparticles as the inorganic discontinuous phase were prepared for CO2/CH4 separation. Membranes were synthesized at filler loading of 0, 5, 10 and 15 wt % via dry phase inversion method. Morphology, chemical bonding and thermal characteristics of membranes were scrutinized utilizing different techniques, namely: Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform InfraRed (FTIR) spectra and Thermogravimetric analysis (TGA) respectively. Membranes gas separation performance was evaluated for CO2 and CH4 gases at 4 bar feed pressure. The highest separation performance was achieved by mixed matrix membrane (MMM) at 5 % loading of TiO2.

The ChArMEx database

Science.gov (United States)

Ferré, Helene; Belmahfoud, Nizar; Boichard, Jean-Luc; Brissebrat, Guillaume; Descloitres, Jacques; Fleury, Laurence; Focsa, Loredana; Henriot, Nicolas; Mastrorillo, Laurence; Mière, Arnaud; Vermeulen, Anne

2014-05-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr/) aims at a scientific assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The project includes long term monitoring of environmental parameters, intensive field campaigns, use of satellite data and modelling studies. Therefore ChARMEx scientists produce and need to access a wide diversity of data. In this context, the objective of the database task is to organize data management, distribution system and services, such as facilitating the exchange of information and stimulating the collaboration between researchers within the ChArMEx community, and beyond. The database relies on a strong collaboration between OMP and ICARE data centres and has been set up in the framework of the Mediterranean Integrated Studies at Regional And Locals Scales (MISTRALS) program data portal. All the data produced by or of interest for the ChArMEx community will be documented in the data catalogue and accessible through the database website: http://mistrals.sedoo.fr/ChArMEx. At present, the ChArMEx database contains about 75 datasets, including 50 in situ datasets (2012 and 2013 campaigns, Ersa background monitoring station), 25 model outputs (dust model intercomparison, MEDCORDEX scenarios), and a high resolution emission inventory over the Mediterranean. Many in situ datasets have been inserted in a relational database, in order to enable more accurate data selection and download of different datasets in a shared format. The database website offers different tools: - A registration procedure which enables any scientist to accept the data policy and apply for a user database account. - A data catalogue that complies with metadata international standards (ISO 19115-19139; INSPIRE European Directive; Global Change Master Directory Thesaurus). - Metadata forms to document

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

Biogenic CH4 and N2O emissions overwhelm land CO2 sink in Asia: Toward a full GHG budget

Science.gov (United States)

Tian, H.

2017-12-01

The recent global assessment indicates the terrestrial biosphere as a net source of greenhouse gases to the atmosphere (Tian et al Nature 2016). The fluxes of greenhouse gases (GHG) vary by region. Both TD and BU approaches indicate that human-caused biogenic fluxes of CO2, CH4 and N2O in the biosphere of Southern Asia led to a large net climate warming effect, because the 100-year cumulative effects of CH4 and N2O emissions together exceed that of the terrestrial CO2 sink. Southern Asia has about 90% of the global rice fields and represents more than 60% of the world's nitrogen fertilizer consumption, with 64%-81% of CH4 emissions and 36%-52% of N2O emissions derived from the agriculture and waste sectors. Given the large footprint of agriculture in Southern Asia, improved fertilizer use efficiency, rice management and animal diets could substantially reduce global agricultural N2O and CH4 emissions. This study highlights the importance of including all three major GHGs in regional climate impact assessments, mitigation option and climate policy development.

Automated CO2, CH4 and N2O Fluxes from Tree Stems and Soils: Magnitudes, Temporal Patterns and Drivers

Science.gov (United States)

Barba, J.; Poyatos, R.; Vargas, R.

2017-12-01

The emissions of the main greenhouse gases (GHG; CO2, CH4 and N2O) through tree stems are still an uncertain component of the total GHG balance of forests. Despite that stem CO2 emissions have been studied for several decades, it is still unclear the drivers and spatiotemporal patterns of CH4 and N2O stem emissions. Additionally, it is unknown how stem emissions could be related to soil physiological processes or environmental conditions. We measured CO2, CH4 and N2O emissions hourly from April to July 2017 at two different heights (75 [LStem] and 150cm [HStem]) of bitternut hickory (Carya cordiformis) trees and adjacent soil locations in a forested area in the Mid Atlantic of the USA. We designed an automated system to continuously measure the three greenhouse gases (GHG) in stems and soils. Stem and soil CO2 emissions showed similar seasonal patterns with an average of 6.56±0.09 (soil), 3.72±0.05 (LStem) and 2.47±0.04 µmols m-2 s-1 (HStem) (mean±95% CI). Soil temperature controlled CO2 fluxes at both daily and seasonal scales (R2>0.5 for all cases), but there was no clear effect of soil moisture. The stems were a clear CH4 source with emissions decreasing with height (0.35±0.02 and 0.25±0.01 nmols m-2 s-1 for LStem and HStem, respectively) with no apparent seasonal pattern, and no clear relationship with environmental drivers (e.g., temperature, moisture). In contrast, soil was a CH4 sink throughout the experiment (-0.55±0.02 nmols m-2 s-1) and its seasonal pattern responded to moisture changes. Despite soil and stem N2O emissions did not show a seasonal pattern or apparent dependency on temperature or moisture, they showed net N2O emissions with a decrease in emissions with stem height (0.29±0.05 for soil, 0.38±0.06 for LStem and 0.28±0.05 nmols m-2 s-1 for HStem). The three GHG emissions decreased with stem height at similar rates (33%, 28% and 27% for CO2, CH4 and N2O, respectively). These results suggest that the gases were not produced in the stem

Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.

Science.gov (United States)

Yan, Chao; Kocevska, Stefani; Krasnoperov, Lev N

2016-08-11

Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

Science.gov (United States)

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

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.

N2O, NO and CH4 exchange, and microbial N turnover over a Mediterranean pine forest soil

Directory of Open Access Journals (Sweden)

P. Rosenkranz

2006-01-01

Full Text Available Trace gas exchange of N2O, NO/NO2 and CH4 between soil and the atmosphere was measured in a typical Mediterranean pine (Pinus pinaster forest during two intensive field campaigns in spring and autumn 2003. Furthermore, gross and net turnover rates of N mineralization and nitrification as well as soil profiles of N2O and CH4 concentrations were determined. For both seasons a weak but significant N2O uptake from the atmosphere into the soil was observed. During the unusually dry and hot spring mean N2O uptake was −4.32 µg N m-2 h-1, whereas during the wet and mild autumn mean N2O uptake was −7.85 µg N m-2 h-1. The observed N2O uptake into the soil was linked to the very low availability of inorganic nitrogen at the study site. Organic layer gross N mineralization decreased from 5.06 mg N kg-1 SDW d-1 in springtime to 2.68 mg N kg-1 SDW d-1 in autumn. Mean NO emission rates were significantly higher in springtime (9.94 µg N m-2 h-1 than in autumn (1.43 µg N m-2 h-1. A significant positive correlation between NO emission rates and gross N mineralization as well as nitrification rates was found. The negative correlation between NO emissions and soil moisture was explained with a stimulation of aerobic NO uptake under N limiting conditions. Since NO2 deposition was continuously higher than NO emission rates the examined forest soil functioned as a net NOx sink. Observed mean net CH4 uptake rates were in spring significantly higher (−73.34 µg C m-2 h-1 than in autumn (−59.67 µg C m-2 h-1. Changes in CH4 uptake rates were strongly negatively correlated with changes in soil moisture. The N2O and CH4 concentrations in different soil depths revealed the organic layer and the upper 0.1 m of mineral soil as the most important soil horizons for N2O and CH4 consumption.

Temporal and spatial variations of soil CO2, CH4 and N2O fluxes at three differently managed grasslands

Directory of Open Access Journals (Sweden)

D. Imer

2013-09-01

Full Text Available A profound understanding of temporal and spatial variabilities of soil carbon dioxide (CO2, methane (CH4 and nitrous oxide (N2O fluxes between terrestrial ecosystems and the atmosphere is needed to reliably quantify these fluxes and to develop future mitigation strategies. For managed grassland ecosystems, temporal and spatial variabilities of these three soil greenhouse gas (GHG fluxes occur due to changes in environmental drivers as well as fertilizer applications, harvests and grazing. To assess how such changes affect soil GHG fluxes at Swiss grassland sites, we studied three sites along an altitudinal gradient that corresponds to a management gradient: from 400 m a.s.l. (intensively managed to 1000 m a.s.l. (moderately intensive managed to 2000 m a.s.l. (extensively managed. The alpine grassland was included to study both effects of extensive management on CH4 and N2O fluxes and the different climate regime occurring at this altitude. Temporal and spatial variabilities of soil GHG fluxes and environmental drivers on various timescales were determined along transects of 16 static soil chambers at each site. All three grasslands were N2O sources, with mean annual soil fluxes ranging from 0.15 to 1.28 nmol m−2 s−1. Contrastingly, all sites were weak CH4 sinks, with soil uptake rates ranging from −0.56 to −0.15 nmol m−2 s−1. Mean annual soil and plant respiration losses of CO2, measured with opaque chambers, ranged from 5.2 to 6.5 μmol m−2 s−1. While the environmental drivers and their respective explanatory power for soil N2O emissions differed considerably among the three grasslands (adjusted r2 ranging from 0.19 to 0.42, CH4 and CO2 soil fluxes were much better constrained (adjusted r2 ranging from 0.46 to 0.80 by soil water content and air temperature, respectively. Throughout the year, spatial heterogeneity was particularly high for soil N2O and CH4 fluxes. We found permanent hot spots for soil N2O emissions as well as

Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

Science.gov (United States)

Xu, Z F; Raghunath, P; Lin, M C

2015-07-16

The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

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

An automated setup to measure paleoatmospheric δ13C-CH4, δ15N-N2O and δ18O-N2O in one ice core sample

NARCIS (Netherlands)

Sperlich, P.; Buizert, C.; Jenk, T.M.; Sapart, C.J.; Prokopiou, M.; Röckmann, T.; Blunier, T.

2013-01-01

Air bubbles in ice core samples represent the only opportunity to study the isotopic variability of paleoatmospheric CH4 and N2O. The highest possible precision in isotope measurements is required to maximize the resolving power for CH4 and N2O sink and source reconstructions. We present a new setup

Straw enhanced CO2 and CH4 but decreased N2O emissions from flooded paddy soils: Changes in microbial community compositions

Science.gov (United States)

Wang, Ning; Yu, Jian-Guang; Zhao, Ya-Hui; Chang, Zhi-Zhou; Shi, Xiao-Xia; Ma, Lena Q.; Li, Hong-Bo

2018-02-01

To explore microbial mechanisms of straw-induced changes in CO2, CH4, and N2O emissions from paddy field, wheat straw was amended to two paddy soils from Taizhou (TZ) and Yixing (YX), China for 60 d under flooded condition. Illumia sequencing was used to characterize shift in bacterial community compositions. Compared to control, 1-5% straw amendment significantly elevated CO2 and CH4 emissions with higher increase at higher application rates, mainly due to increased soil DOC concentrations. In contrast, straw amendment decreased N2O emission. Considering CO2, CH4, and N2O emissions as a whole, an overall increase in global warming potential was observed with straw amendment. Total CO2 and CH4 emissions from straw-amended soils were significantly higher for YX than TZ soil, suggesting that straw-induced greenhouse gas emissions depended on soil characteristics. The abundance of C-turnover bacteria Firmicutes increased from 28-41% to 54-77% with straw amendment, thereby increasing CO2 and CH4 emissions. However, straw amendment reduced the abundance of denitrifying bacteria Proteobacteria from 18% to 7.2-13% or increased the abundance of N2O reducing bacteria Clostridium from 7.6-11% to 13-30%, thereby decreasing N2O emission. The results suggested straw amendment strongly influenced greenhouse gas emissions via alerting soil properties and bacterial community compositions. Future field application is needed to ascertain the effects of straw return on greenhouse gas emissions.

Electron paramagnetic resonance of gamma irradiated (CH3)3NHClO4 and CH3NH3ClO4 single crystals

International Nuclear Information System (INIS)

Yavuz, Metin; Koeksal, Fevzi

1999-01-01

Gamma irradiation damage centers in (CH 3 ) 3 NHClO 4 and CH 3 NH 3 ClO 4 single crystals have been investigated at room temperature by the electron paramagnetic resonance (EPR) technique. It has been found that γ-irradiation produces the (CH 3 ) 3 N + radical in the first, and NH + 3 and ClO 3 radicals in the second compound. The EPR parameters of the observed radicals have been determined and discussed

Negative ions formed in N₂/CH₄/Ar discharge – a simulation of Titan's atmosphere chemistry

OpenAIRE

Horvath, G.; Aranda-Gonzalvo, Y.; Mason, N. J.; Zahoran, M.; Matejcik, S.

2010-01-01

The formation of negative ions produced in a negative point-to-plane corona discharge fed by a Ar/N2//CH4/ gas mixture has been studied using mass spectrometry. The measurements were carried out in flowing regime at ambient temperature and a reduced pressure of 460 mbar. The CN ? anion has been found to be the most dominant negative ion in the discharge and is believed to be the precursor of heavier negative ions such as C3/N ? and C5/N ? . The most likely pathway for the formation of such mo...

An overview of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx)

Science.gov (United States)

Dulac, François

2014-05-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr) is a French initiative of the MISTRALS meta-programme (Mediterranean Integrated Studies at Regional And Locals Scales, http://www.mistrals-home.org). It federates a great number of national and international cooperative research actions aiming at a scientific assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The target is short-lived particulate and gaseous tropospheric trace species which are the cause of poor air quality events, have two-way interactions with climate, or impact the marine biogeochemistry, in a context of strong regional anthropogenic and climatic pressures. The six ChArMEx work packages include Emissions, Chemical processes and ageing, Transport processes and air quality, Aerosol-radiation-climate interactions, Deposition, and Present and future variability and trends. For several years, efforts have been deployed in several countries to develop (i) a network of relevant stations for atmospheric chemistry at background sites on islands and continental coasts around the basin and (ii) several intensive field campaigns including the operation of surface supersites and various instrumented mobile platforms (large and ultra-light aircraft, sounding and drifting balloons, ZeroCO2 sailboat). This presentation is an attempt to provide an overview of the various experimental, remote sensing and modelling efforts produced and to highlight major findings, by referencing more detailed ChArMEx presentations given in this conference and recently published or submitted papers. During the first phase of the project experimental efforts have been mainly concentrated on the western basin. Plans for the 2nd phase of ChArMEx, more dedicated towards the eastern basin, will also be given. In particular we plan to develop monitoring activities at

Phosphinodi(benzylsilane) PhP{(o-C6H4CH2)SiMe2H}2: a versatile "PSi2Hx" pincer-type ligand at ruthenium.

Science.gov (United States)

Montiel-Palma, Virginia; Muñoz-Hernández, Miguel A; Cuevas-Chávez, Cynthia A; Vendier, Laure; Grellier, Mary; Sabo-Etienne, Sylviane

2013-09-03

The synthesis of the new phosphinodi(benzylsilane) compound PhP{(o-C6H4CH2)SiMe2H}2 (1) is achieved in a one-pot reaction from the corresponding phenylbis(o-tolylphosphine). Compound 1 acts as a pincer-type ligand capable of adopting different coordination modes at Ru through different extents of Si-H bond activation as demonstrated by a combination of X-ray diffraction analysis, density functional theory calculations, and multinuclear NMR spectroscopy. Reaction of 1 with RuH2(H2)2(PCy3)2 (2) yields quantitatively [RuH2{[η(2)-(HSiMe2)-CH2-o-C6H4]2PPh}(PCy3)] (3), a complex stabilized by two rare high order ε-agostic Si-H bonds and involved in terminal hydride/η(2)-Si-H exchange processes. A small free energy of reaction (ΔrG298 = +16.9 kJ mol(-1)) was computed for dihydrogen loss from 3 with concomitant formation of the 16-electron species [RuH{[η(2)-(HSiMe2)-CH2-o-C6H4]PPh[CH2-o-C6H4SiMe2]}(PCy3)] (4). Complex 4 features an unprecedented (29)Si NMR decoalescence process. The dehydrogenation process is fully reversible under standard conditions (1 bar, 298 K).

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...

A Study on Production of Carbon Nanotubes by CH4 Decomposition over LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Carbon nanotubes (CNTs) of narrow size distribution can be abundantly produced in the catalytic decomposition of CH4 over pre-reduced LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4.The CNTs obtained were characterized by means of transmission electron microscopy (TEM).Thermal oxidation of CNTs in air was monitored thermogravimetrically (TG). The resultsrevealed that a lower La/Ni ratio of the catalysts would lead to a wider diameter distribution and a higher degree of graphitic nature.

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.

Summer fluxes of atmospheric greenhouse gases N{sub 2}O, CH{sub 4} and CO{sub 2} from mangrove soil in South China

Energy Technology Data Exchange (ETDEWEB)

Chen, G.C. [Department of Biology and Chemistry, City University of Hong Kong, Hong Kong SAR (China); Tam, N.F.Y., E-mail: bhntam@cityu.edu.hk [Department of Biology and Chemistry, City University of Hong Kong, Hong Kong SAR (China); Ye, Y. [State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen, Fujian (China)

2010-06-01

The atmospheric fluxes of N{sub 2}O, CH{sub 4} and CO{sub 2} from the soil in four mangrove swamps in Shenzhen and Hong Kong, South China were investigated in the summer of 2008. The fluxes ranged from 0.14 to 23.83 {mu}mol m{sup -2} h{sup -1}, 11.9 to 5168.6 {mu}mol m{sup -2} h{sup -1} and 0.69 to 20.56 mmol m{sup -2} h{sup -1} for N{sub 2}O, CH{sub 4} and CO{sub 2}, respectively. Futian mangrove swamp in Shenzhen had the highest greenhouse gas fluxes, followed by Mai Po mangrove in Hong Kong. Sha Kong Tsuen and Yung Shue O mangroves in Hong Kong had similar, low fluxes. The differences in both N{sub 2}O and CH{sub 4} fluxes among different tidal positions, the landward, seaward and bare mudflat, in each swamp were insignificant. The N{sub 2}O and CO{sub 2} fluxes were positively correlated with the soil organic carbon, total nitrogen, total phosphate, total iron and NH{sub 4}{sup +}-N contents, as well as the soil porosity. However, only soil NH{sub 4}{sup +}-N concentration had significant effects on CH{sub 4} fluxes.

Continuous multi-plot measurements of CO2, CH4, N2O and H2O in a managed boreal forest - The importance of accounting for all greenhouse gases

Science.gov (United States)

Vestin, P.; Mölder, M.; Sundqvist, E.; Båth, A.; Lehner, I.; Weslien, P.; Klemedtsson, L.; Lindroth, A.

2015-12-01

In order to assess the effects of different management practices on the exchange of greenhouse gases (GHG), it is desirable to perform repeated and parallel measurements on both experimental and control plots. Here we demonstrate how a system system combining eddy covariance and gradient techniques can be used to perform this assessment in a managed forest ecosystem.The net effects of clear-cutting and stump harvesting on GHG fluxes were studied at the ICOS site Norunda, Sweden. Micrometeorological measurements (i.e., flux-gradient measurements in 3 m tall towers) allowed for quantification of CO2, CH4 and H2O fluxes (from May 2010) as well as N2O and H2O fluxes (from June 2011) at two stump harvested plots and two control plots. There was one wetter and one drier plot of each treatment. Air was continuously sampled at two heights in the towers and gas concentrations were analyzed for CH4, CO2, H2O (LGR DLT-100, Los Gatos Research) and N2O, H2O (QCL Mini Monitor, Aerodyne Research). Friction velocities and sensible heat fluxes were measured by sonic anemometers (Gill Windmaster, Gill Instruments Ltd). Automatic chamber measurements (CO2, CH4, H2O) were carried out in the adjacent forest stand and at the clear-cut during 2010.Average CO2 emissions for the first year ranged between 14.4-20.2 ton CO2 ha-1 yr-1. The clear-cut became waterlogged after harvest and a comparison of flux-gradient data and chamber data (from the adjacent forest stand) indicated a switch from a weak CH4 sink to a significant source at all plots. The CH4 emissions ranged between 0.8-4.5 ton CO2-eq. ha-1 yr-1. N2O emissions ranged between 0.4-2.6 ton CO2-eq. ha-1 yr-1. Enhanced N2O emission on the drier stump harvested plot was the only clear treatment effect on GHG fluxes that was observed. Mean CH4 and N2O emissions for the first year of measurements amounted up to 29% and 20% of the mean annual CO2 emissions, respectively. This highlights the importance of including all GHGs when assessing

Transient infrared absorption of t-CH3C(O)OO, c-CH3C(O)OO, and α-lactone recorded in gaseous reactions of CH3CO and O2

Science.gov (United States)

Chen, Sun-Yang; Lee, Yuan-Pern

2010-03-01

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH3CO and O2; IR absorption spectra of CH3C(O)OO and α-lactone were observed. Absorption bands with origins at 1851±1, 1372±2, 1169±6, and 1102±3 cm-1 are attributed to t-CH3C(O)OO, and those at 1862±3, 1142±4, and 1078±6 cm-1 are assigned to c-CH3C(O)OO. A weak band near 1960 cm-1 is assigned to α-lactone, cyc-CH2C(O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH3C(O)OO is more stable than c-CH3C(O)OO by 3±2 kJ mol-1. Based on these observations, the branching ratio for the OH+α-lactone channel of the CH3CO+O2 reaction is estimated to be 0.04±0.01 under 100 Torr of O2 at 298 K. A simple kinetic model is employed to account for the decay of CH3C(O)OO.

Transient infrared absorption of t-CH3C(O)OO, c-CH3C(O)OO, and alpha-lactone recorded in gaseous reactions of CH3CO and O2.

Science.gov (United States)

Chen, Sun-Yang; Lee, Yuan-Pern

2010-03-21

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH(3)CO and O(2); IR absorption spectra of CH(3)C(O)OO and alpha-lactone were observed. Absorption bands with origins at 1851+/-1, 1372+/-2, 1169+/-6, and 1102+/-3 cm(-1) are attributed to t-CH(3)C(O)OO, and those at 1862+/-3, 1142+/-4, and 1078+/-6 cm(-1) are assigned to c-CH(3)C(O)OO. A weak band near 1960 cm(-1) is assigned to alpha-lactone, cyc-CH(2)C(=O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH(3)C(O)OO is more stable than c-CH(3)C(O)OO by 3+/-2 kJ mol(-1). Based on these observations, the branching ratio for the OH+alpha-lactone channel of the CH(3)CO+O(2) reaction is estimated to be 0.04+/-0.01 under 100 Torr of O(2) at 298 K. A simple kinetic model is employed to account for the decay of CH(3)C(O)OO.

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.

Occurrence of greenhouse gases (CO2, N2O and CH4) in groundwater of the Walloon Region (Belgium).

Science.gov (United States)

Jurado, Anna; Borges, Alberto V.; Pujades, Estanislao; Hakoun, Vivien; Knöller, Kay; Brouyère, Serge

2017-04-01

Greenhouse gases (GHGs) are an environmental problem because their concentrations in the atmosphere have continuously risen since the industrial revolution. They can be indirectly transferred to the atmosphere through groundwater discharge into surface water bodies such as rivers. However, their occurrence is poorly evaluated in groundwater. The aim of this work is to identify the hydrogeological contexts (e.g., chalk and limestone aquifers) and the most conductive conditions for the generation of GHGs in groundwater at a regional scale. To this end, carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) concentrations, major and minor elements and environmental isotopes were monitored in several groundwater bodies of the Walloon Region (Belgium) from September 2014 to June 2016. The concentrations of GHGs in groundwater ranged from 1769 to 100519 ppm for the partial pressure of CO2 and from 0 to 1064 nmol/L and 1 to 37062 nmol/L for CH4 and N2O respectively. Overall, groundwater was supersaturated in GHGs with respect to atmospheric equilibrium, suggesting that groundwater contribute to the atmospheric GHGs budget. Prior inspection of the data suggested that N2O in groundwater can be produced by denitrification and nitrification. The most suitable conditions for the accumulation of N2O are promoted by intermediate dissolved oxygen concentrations (2.5-3 mg L-1) and the availability of nitrate (NO3-). These observations will be compared with the isotopes of NO3-. CH4 was less detected and at lower concentration than N2O, suggesting that groundwater redox conditions are not reducing enough to promoted the production of CH4. The results will be presented and discussed in detail in the presentation.

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...

Spectroscopic diagnostics and modeling of Ar/H2/CH4 microwave discharges used for nanocrystalline diamond deposition

International Nuclear Information System (INIS)

Lombardi, G.; Hassouni, K.; Benedic, F.; Mohasseb, F.; Roepcke, J.; Gicquel, A.

2004-01-01

In this paper Ar/H 2 /CH 4 microwave discharges used for nanocrystalline diamond chemical vapor deposition in a bell-jar cavity reactor were characterized by both experimental and modeling investigations. Discharges containing 1% CH 4 and H 2 percentages ranging between 2% and 7% were analyzed as a function of the input microwave power under a pressure of 200 mbar. Emission spectroscopy and broadband absorption spectroscopy were carried out in the UV-visible spectral range in order to estimate the gas temperature and the C 2 density within the plasma. Infrared tunable diode laser absorption spectroscopy was achieved in order to measure the mole fractions of carbon-containing species such as CH 4 , C 2 H 2 , and C 2 H 6 . A thermochemical model was developed and used in order to estimate the discharge composition, the gas temperature, and the average electron energy in the frame of a quasihomogeneous plasma assumption. Experiments and calculations yielded consistent results with respect to plasma temperature and composition. A relatively high gas temperature ranging between 3000 and 4000 K is found for the investigated discharge conditions. The C 2 density estimated from both experiments and modeling are quite high compared with what is generally reported in the literature for the same kind of plasma system. It ranges between 10 13 and 10 14 cm -3 in the investigated power range. Infrared absorption measurements and model predictions indicate quite low densities of methane and acetylene, while the atomic carbon density calculated by the model ranges between 10 13 and 10 15 cm -3 . The methane and hydrogen introduced in the feed gas are subject to a strong dissociation, which results in a surprisingly high H-atom population with mole fraction ranging between 0.04 and 0.16. Result analysis shows that the power coupling efficiency would range between 70% and 90%, which may at least explain the relatively high values obtained, as compared with those reported in the

Linking soil O2, CO2, and CH4 concentrations in a wetland soil

DEFF Research Database (Denmark)

Elberling, Bo; Jensen, Louise Askær; Jørgensen, Christian Juncher

2011-01-01

and CH4 were measured in the laboratory during flooding of soil columns using a combination of planar O2 optodes and membrane inlet mass spectrometry. Microsensors were used to assess apparent diffusivity under both field and laboratory conditions. Gas concentration profiles were analyzed...... plants tissue on soil gas dynamics and greenhouse gas emissions following marked changes in water level....

Wastes Management Can Minimize CH4 and N2O Emissions from Wetlands in Indonesia

Directory of Open Access Journals (Sweden)

Abdul Hadi

2015-07-01

Full Text Available Paddy (Oriza sativa L. and Oil palm (Elaeis guineensis Jack are two important crops and are potential to produce wastes which may lead to huge greenhouse gas emissions if they are not managed properly.  Open burning and conventional composting are commonly practiced by farmers and/or planters to managed agricultural wastes in Indonesia.  A series of research has been carried out  to elucidate (1 the reductions of CH4 and N2O due to incertion of a catalitic converter on burning kiln, (2 the best composting technique of oil palm field wastes, and (3 the effects of oil palm field wastes compost application in oil palm fields and of paddy field wastes biochar in integrated oil palm-paddy fields.  The results showed that CH4 and N2O emissions from paddy field wastes (i.e., rice straw or rice husk was lower than that from oil palm empty fruit bunch (EFB.  Furthermore, insertion of a catalytic converter into pyrolysis installation reduced the CO2, CH4 and N2O emissions from paddy field wastes as much as 14.5, 17.8 and 11.1%, respectively.  Incorporation of EFB compost did not increase greenhouse gas emission from oil palm fields. These results suggest that biochar and EFB compost can be practiced to manage agricultural wastes in Indonesia.

Adsorption properties of CO, H{sub 2} and CH{sub 4} over Pd/γ-Al{sub 2}O{sub 3} catalyst: A density functional study

Energy Technology Data Exchange (ETDEWEB)

Song, Zijian; Wang, Ben, E-mail: benwang@hust.edu.cn; Yu, Jie; Ma, Chuan; Qu, Qinggong; Zeng, Zhao; Xiang, Jun; Hu, Song; Sun, Lushi, E-mail: sunlushi@hust.edu.cn

2016-11-30

Highlights: • Model of dimer Pd supported on γ-Al{sub 2}O{sub 3} (1 1 0) surface was established. • CO, H{sub 2} and CH{sub 4} adsorption on clean γ-Al{sub 2}O{sub 3} and on Pd/γ-Al{sub 2}O{sub 3} surface was studied by DFT calculations. • CO, H{sub 2} and CH{sub 4} adsorptions are energetically more favorable in the presence of dimer Pd. • Mechanism of CO, H{sub 2} and CH{sub 4} adsorption on Pd/γ-Al{sub 2}O{sub 3} (1 1 0) surface was explained. - Abstract: Density functional theory (DFT) calculations were employed to investigate the adsorption characteristics of carbon monoxide (CO), hydrogen (H{sub 2}), and methane (CH{sub 4}) on the surface of clean γ-Al{sub 2}O{sub 3} and Pd supported γ-Al{sub 2}O{sub 3}, which is of significant for catalytic combustion. The adsorption intensities of the three gas molecules in pure γ-Al{sub 2}O{sub 3} (1 1 0) and Pd/γ-Al{sub 2}O{sub 3} (1 1 0) were in the order of CO > H{sub 2} > CH{sub 4}. The corresponding adsorption energies on the Pd/γ-Al{sub 2}O{sub 3} (1 1 0) surface were at least three times higher than those on γ-Al{sub 2}O{sub 3} (1 1 0). Anlysis of Mulliken population and partial density of states (PDOS) showed that the adsorption mechanisms were as follow: (a) CO stably adsorbed on the bridge site of dimer Pd with two C−Pd bonds because of charges transfer from the surface to CO, and the triple bond (C≡O) was broken to a double bond (C=O); (b) H{sub 2} was dissociated into hydrogen atoms on the dimer Pd and produced a stable planar configuration; and (c) the tetrahedral structure of CH{sub 4} was destroyed on the surface and formed a −CH{sub 3} species bonded to the Pd atom, which contributes to the orbital hybridization between C and Pd atoms.

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.

Determination of gas temperature and C2 absolute density in Ar/H2/CH4 microwave discharges used for nanocrystalline diamond deposition from the C2 Mulliken system

International Nuclear Information System (INIS)

Lombardi, G; Benedic, F; Mohasseb, F; Hassouni, K; Gicquel, A

2004-01-01

The spectroscopic characterization of Ar/H 2 /CH 4 discharges suitable for the synthesis of nanocrystalline diamond using the microwave plasma assisted chemical vapour deposition process is reported. The experiments are realized in a moderate-pressure bell jar reactor, where discharges are ignited using a microwave cavity coupling system. The concentration of CH 4 is maintained at 1% and the coupled set of hydrogen concentration/microwave power (MWP) ranges from 2%/500 W to 7%/800 W at a pressure of 200 mbar. Emission spectroscopy and broadband absorption spectroscopy studies are carried out on the C 2 (D I SIGMA + u -CHI I SIGMA + g ) Mulliken system and the C 2 (d 3 Π g -a 3 Π u ) Swan system in order to determine the gas temperature and the C 2 absolute density within the plasma. For this purpose, and since the Swan system is quite well-known, much importance is devoted to the achievement of a detailed simulation of the Mulliken system, which allows the determination of both the rotational temperature and the density of the CHI I SIGMA + g ground state, as well as the rotational temperature of the D I SIGMA + u state, from experimental data. All the experimental values are compared to those predicted by a thermochemical model developed to describe Ar/H 2 /CH 4 microwave discharges under quasi-homogeneous plasma assumption. This comparison shows a reasonable agreement between the values measured from the C 2 Mulliken system, those measured from the C 2 Swan system and that calculated from plasma modelling, especially at low hydrogen concentration/MWP. These consistent results show that the use of the Mulliken system leads to fairly good estimates of the gas temperature and of the C 2 absolute density. The relatively high gas temperatures found for the conditions investigated, typically between 3000 K and 4000 K, are attributed to the low thermal conductivity of argon that may limit thermal losses to the substrate surface and reactor wall. The measured C 2

Stable isotope ratios of the atmospheric CH4, CO2 and N2O in Tokai-mura

International Nuclear Information System (INIS)

Porntepkasemsan, Boonsom; Andoh, Mariko A.; Amano, Hikaru

2000-11-01

This report presents the results and interpretation of stable isotope ratios of the atmospheric CH 4 , CO 2 and N 2 O from a variety of sources in Tokai-mura. The seasonal changes of δ 13 CH 4 , δ 13 CO 2 and δ 15 N 2 O were determined under in-situ conditions in four sampling sites and one control site. Such measurements are expected to provide a useful means of estimating the transport mechanisms of the three trace gases in the environment. These isotopic signatures were analyzed by Isotope Ratio Mass Spectrometer (IRMS, Micromass Isoprime). Our data showed the significant seasonal fluctuation in the Hosoura rice paddy during the entire growing season in 1999. Possible causes for the variation are postulated. Additional measurements on soil properties and on organic δ 13 C in rice plant are suggested. Cited outstanding original papers are summarized in the references. (author)

Lipon thin films grown by plasma-enhanced metalorganic chemical vapor deposition in a N{sub 2}-H{sub 2}-Ar gas mixture

Energy Technology Data Exchange (ETDEWEB)

Meda, Lamartine, E-mail: LMeda@xula.edu [Department of Chemistry, Xavier University of Louisiana, 1 Drexel Drive, New Orleans, LA, 70125 (United States); Maxie, Eleston E. [Excellatron Solid State LLC, 263 Decatur Street, Atlanta, GA 30312 (United States)

2012-01-01

Lithium phosphorus oxynitride (Lipon) thin films have been deposited by a plasma-enhanced metalorganic chemical vapor deposition method. Lipon thin films were deposited on approximately 0.2 {mu}m thick Au-coated alumina substrates in a N{sub 2}-H{sub 2}-Ar plasma at 13.56 MHz, a power of 150 W, and at 180 Degree-Sign C using triethyl phosphate [(CH{sub 2}CH{sub 3}){sub 3}PO{sub 4}] and lithium tert-butoxide [(LiOC(CH{sub 3}){sub 3}] precursors. Lipon growth rates ranged from 10 to 42 nm/min and thicknesses varied from 1 to 2.5 {mu}m. X-ray powder diffraction showed that the films were amorphous, and X-ray photoelectron spectroscopy (XPS) revealed approximately 4 at.% N in the films. The ionic conductivity of Lipon was measured by electrochemical impedance spectroscopy to be approximately 1.02 {mu}S/cm, which is consistent with the ionic conductivity of Lipon deposited by radio frequency magnetron sputtering of Li{sub 3}PO{sub 4} targets in either mixed Ar-N{sub 2} or pure N{sub 2} atmosphere. Attempts to deposit Lipon in a N{sub 2}-O{sub 2}-Ar plasma resulted in the growth of Li{sub 3}PO{sub 4} thin films. The XPS analysis shows no C and N atom peaks. Due to the high impedance of these films, reliable conductivity measurements could not be obtained for films grown in N{sub 2}-O{sub 2}-Ar plasma.

Effects of elevated atmospheric CO2, prolonged summer drought and temperature increase on N2O and CH4 fluxes in a temperate heathland

DEFF Research Database (Denmark)

Carter, Mette Sustmann; Ambus, Per; Albert, Kristian Rost

2011-01-01

In temperate regions, climate change is predicted to increase annual mean temperature and intensify the duration and frequency of summer droughts, which together with elevated atmospheric carbon dioxide (CO2) concentrations, may affect the exchange of nitrous oxide (N2O) and methane (CH4) between...... terrestrial ecosystems and the atmosphere. We report results from the CLIMAITE experiment, where the effects of these three climate change parameters were investigated solely and in all combinations in a temperate heathland. Field measurements of N2O and CH4 fluxes took place 1–2 years after the climate...... change manipulations were initiated. The soil was generally a net sink for atmospheric CH4. Elevated temperature (T) increased the CH4 uptake by on average 10 μg C m−2 h−1, corresponding to a rise in the uptake rate of about 20%. However, during winter elevated CO2 (CO2) reduced the CH4 uptake, which...

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Science.gov (United States)

Circone, S.; Kirby, S.H.; Stern, L.A.

2006-01-01

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions.

Energy Technology Data Exchange (ETDEWEB)

Wang, Yifeng [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2018-02-01

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO₂ and H₂O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH₄) during hydrofracturing and gas extraction. Note that liquid or supercritical CO₂ has been suggested as an alternative fluid for subsurface fracturing such that CO₂ enhanced gas recovery can also serve as a CO₂ sequestration process. Limited data indicate that CO₂ may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH₄ in shale matrix. Therefore, fundamental understanding of CH₄-CO₂-H₂O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO₂ sequestration. This project focuses on the systematic study of CH₄-CO₂-H₂O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

Suitability of quantum cascade laser spectroscopy for CH4 and N2O eddy covariance flux measurements

Directory of Open Access Journals (Sweden)

A. T. Vermeulen

2007-08-01

Full Text Available A quantum cascade laser spectrometer was evaluated for eddy covariance flux measurements of CH4 and N2O using three months of continuous measurements at a field site. The required criteria for eddy covariance flux measurements including continuity, sampling frequency, precision and stationarity were examined. The system operated continuously at a dairy farm on peat grassland in the Netherlands from 17 August to 6 November 2006. An automatic liquid nitrogen filling system for the infrared detector was employed to provide unattended operation of the system. The electronic sampling frequency was 10 Hz, however, the flow response time was 0.08 s, which corresponds to a bandwidth of 2 Hz. A precision of 2.9 and 0.5 ppb Hz−1/2 was obtained for CH4 and N2O, respectively. Accuracy was assured by frequent calibrations using low and high standard additions. Drifts in the system were compensated by using a 120 s running mean filter. The average CH4 and N2O exchange was 512 ngC m−2 s−1 (2.46 mg m−2 hr−1 and 52 ngN m−2 s−1 (0.29 mg m−2 hr−1. Given that 40% of the total N2O emission was due to a fertilizing event.

Optimum O2:CH4 Ratio Promotes the Synergy between Aerobic Methanotrophs and Denitrifiers to Enhance Nitrogen Removal

Directory of Open Access Journals (Sweden)

Jing Zhu

2017-06-01

Full Text Available The O2:CH4 ratio significantly effects nitrogen removal in mixed cultures where aerobic methane oxidation is coupled with denitrification (AME-D. The goal of this study was to investigate nitrogen removal of the AME-D process at four different O2:CH4 ratios [0, 0.05, 0.25, and 1 (v/v]. In batch tests, the highest denitrifying activity was observed when the O2:CH4 ratio was 0.25. At this ratio, the methanotrophs produced sufficient carbon sources for denitrifiers and the oxygen level did not inhibit nitrite removal. The results indicated that the synergy between methanotrophs and denitrifiers was significantly improved, thereby achieving a greater capacity of nitrogen removal. Based on thermodynamic and chemical analyses, methanol, butyrate, and formaldehyde could be the main trophic links of AME-D process in our study. Our research provides valuable information for improving the practical application of the AME-D systems.

Greenhouse impact of CH{sub 4}, N{sub 2}O and CFC emissions in Finland and its control potential

Energy Technology Data Exchange (ETDEWEB)

Pipatti, R.; Savolainen, I.; Sinisalo, J. [VTT Energy, Espoo (Finland)

1995-12-31

Methane (CH{sub 4}), nitrous oxide (N{sub 2}O) and chlorofluorocarbon (CFC) emissions contribute considerably to the anthropogenic enhancement of Earth`s greenhouse effect. The limitation of atmospheric concentrations of CH{sub 4} and N{sub 2}O is considered important also in the Climate Convention. Chlorine released from the CFCs in the stratosphere destroys ozone (O{sub 3}) and the emissions are therefore regulated with the Montreal Protocol. The greenhouse impact of CFCs might be, at least to some extent, compensated by the depletion of O{sub 3} which is also a greenhouse gas. The objective of the presentation is to assess the role of anthropogenic CH{sub 4}, N{sub 2}O, and CFC emissions in the total direct greenhouse impact due to human activities in Finland. The emission estimates for the gases are presented, as well as scenarios for emission history, future development and control potential. The greenhouse impact of the gases is compared with that of carbon dioxide (CO{sub 2}) emissions in Finland. (author)

Greenhouse impact of CH{sub 4}, N{sub 2}O and CFC emissions in Finland and its control potential

Energy Technology Data Exchange (ETDEWEB)

Pipatti, R; Savolainen, I; Sinisalo, J [VTT Energy, Espoo (Finland)

1996-12-31

Methane (CH{sub 4}), nitrous oxide (N{sub 2}O) and chlorofluorocarbon (CFC) emissions contribute considerably to the anthropogenic enhancement of Earth`s greenhouse effect. The limitation of atmospheric concentrations of CH{sub 4} and N{sub 2}O is considered important also in the Climate Convention. Chlorine released from the CFCs in the stratosphere destroys ozone (O{sub 3}) and the emissions are therefore regulated with the Montreal Protocol. The greenhouse impact of CFCs might be, at least to some extent, compensated by the depletion of O{sub 3} which is also a greenhouse gas. The objective of the presentation is to assess the role of anthropogenic CH{sub 4}, N{sub 2}O, and CFC emissions in the total direct greenhouse impact due to human activities in Finland. The emission estimates for the gases are presented, as well as scenarios for emission history, future development and control potential. The greenhouse impact of the gases is compared with that of carbon dioxide (CO{sub 2}) emissions in Finland. (author)

The emissions and soil concentrations of N2O and CH4 from natural soil temperature gradients in a volcanic area in southwest Iceland

Science.gov (United States)

Maljanen, Marja; Yli-Moijala, Heli; Leblans, Niki I. W.; De Boeck, Hans J.; Bjarnadóttir, Brynhildur; Sigurdsson, Bjarni D.

2016-04-01

We studied nitrous oxide (N2O) and methane (CH4) emissions along three natural geothermal soil temperature (Ts) gradients in a volcanic area in southwest Iceland. Two of the gradients (on a grassland and a forest site, respectively) were recently formed (in May 2008). The third gradient, a grassland site, had been subjected to long-term soil warming (over 30 years, and probably centuries). Nitrous oxide and methane emissions were measured along the temperature gradients using the static chamber method and also soil gas concentrations were studied. With a moderate soil temperature increase (up to +5 °C) there were no significant increase in gas flux rates in any of the sites but an increase of 20 to 45 °C induced an increase in both N2O and CH4 emissions. The measured N2O emissions (up to 2600 μg N2O m-2 h-1) from the warmest plots were about two magnitudes higher compared with the coolest plots (less than 20 μg N2O m-2 h-1). While a net uptake of CH4 was measured in the coolest plots (up to -0.15 mg CH4 m-2 h-1), a net emission of CH4 was measured from the warmest plots (up to 1.3 mg CH4 m-2 h-1). Soil CH4 concentrations decreased first with a moderate (up to +5 °C) increase in Ts, but above that threshold increased significantly. The soil N2O concentration at depths from 5 to 20 cm increased with increasing Ts, indicating enhanced N-turnover. Further, there was a clear decrease in soil organic matter (SOM), C- and N concentration with increasing Ts at all sites. One should note, however, that a part of the N2O emitted from the warmest plots may be partly geothermally derived, as was revealed by 15N2O isotope studies. These natural Ts gradients show that the emission of N2O and CH4 can increase significantly when Ts increases considerably. This implies that these geothermally active sites can act as local hot spots for CH4 and N2O emissions.

Response of CH4 and N2O emissions and wheat yields to tillage method changes in the North China plain.

Directory of Open Access Journals (Sweden)

Shenzhong Tian

Full Text Available The objective of this study was to quantify soil methane (CH(4 and nitrous oxide (N(2O emissions when converting from minimum and no-tillage systems to subsoiling (tilled soil to a depth of 40 cm to 45 cm in the North China Plain. The relationships between CH(4 and N(2O flux and soil temperature, moisture, NH(4 (+-N, organic carbon (SOC and pH were investigated over 18 months using a split-plot design. The soil absorption of CH(4 appeared to increase after conversion from no-tillage (NT to subsoiling (NTS, from harrow tillage (HT to subsoiling (HTS and from rotary tillage (RT to subsoiling (RTS. N(2O emissions also increased after conversion. Furthermore, after conversion to subsoiling, the combined global warming potential (GWP of CH(4 and N(2O increased by approximately 0.05 kg CO(2 ha(-1 for HTS, 0.02 kg CO(2 ha(-1 for RTS and 0.23 kg CO(2 ha(-1 for NTS. Soil temperature, moisture, SOC, NH(4 (+-N and pH also changed after conversion to subsoiling. These changes were correlated with CH(4 uptake and N(2O emissions. However, there was no significant correlation between N(2O emissions and soil temperature in this study. The grain yields of wheat improved after conversion to subsoiling. Under HTS, RTS and NTS, the average grain yield was elevated by approximately 42.5%, 27.8% and 60.3% respectively. Our findings indicate that RTS and HTS would be ideal rotation tillage systems to balance GWP decreases and grain yield improvements in the North China Plain region.

Comparisons of continuous atmospheric CH4, CO2 and N2O measurements - results from a travelling instrument campaign at Mace Head

International Nuclear Information System (INIS)

Vardag, S.N.; Hammer, S.; Levin, I.; O'Doherty, S.; Spain, T.G.; Wastine, B.; Jordan, A.

2014-01-01

A 2-month measurement campaign with a Fourier transform infrared analyser as a travelling comparison instrument (TCI) was performed at the Advanced Global Atmospheric Gases Experiment (AGAGE) and World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station at Mace Head, Ireland. The aim was to evaluate the compatibility of atmospheric methane (CH 4 ), carbon dioxide (CO 2 ) and nitrous oxide (N 2 O) measurements of the routine station instrumentation, consisting of a gas chromatograph (GC) for CH 4 and N 2 O as well as a cavity ring-down spectroscopy (CRDS) system for CH 4 and CO 2 . The advantage of a TCI approach for quality control is that the comparison covers the entire ambient air measurement system, including the sample intake system and the data evaluation process. For initial quality and performance control, the TCI was run in parallel with the Heidelberg GC before and after the measurement campaign at Mace Head. Median differences between the Heidelberg GC and the TCI were well within the WMO inter-laboratory compatibility target for all three greenhouse gases. At Mace Head, the median difference between the station GC and the TCI were -0.04 nmol mol -1 for CH 4 and -0.37 nmol mol -1 for N 2 O (GC-TCI). For N 2 O, a similar difference (-0.40 nmol mol -1 ) was found when measuring surveillance or working gas cylinders with both instruments. This suggests that the difference observed in ambient air originates from a calibration offset that could partly be due to a difference between the WMON2O X2006a reference scale used for the TCI and the Scripps Institution of Oceanography (SIO-1998) scale used at Mace Head and in the whole AGAGE network. Median differences between the CRDS G1301 and the TCI at Mace Head were 0.12 nmol mol -1 for CH 4 and 0.14 μmol mol -1 for CO 2 (CRDS G1301 - TCI). The difference between both instruments for CO 2 could not be explained, as direct measurements of calibration gases show no such difference. The CH 4

CO2, CH4 and N2O fluxes from soil of a burned grassland in Central Africa

Directory of Open Access Journals (Sweden)

R. Valentini

2010-11-01

Full Text Available The impact of fire on soil fluxes of CO2, CH4 and N2O was investigated in a tropical grassland in Congo Brazzaville during two field campaigns in 2007–2008. The first campaign was conducted in the middle of the dry season and the second at the end of the growing season, respectively one and eight months after burning. Gas fluxes and several soil parameters were measured in each campaign from burned plots and from a close-by control area preserved from fire. Rain events were simulated at each campaign to evaluate the magnitude and duration of the generated gas flux pulses. In laboratory experiments, soil samples from field plots were analysed for microbial biomass, net N mineralization, net nitrification, N2O, NO and CO2 emissions under different water and temperature soil regimes. One month after burning, field CO2 emissions were significantly lower in burned plots than in the control plots, the average daily CH4 flux shifted from net emission in the unburned area to net consumption in burned plots, no significant effect of fire was observed on soil N2O fluxes. Eight months after burning, the average daily fluxes of CO2, CH4 and N2O measured in control and burned plots were not significantly different. In laboratory, N2O fluxes from soil of burned plots were significantly higher than fluxes from soil of unburned plots only above 70% of maximum soil water holding capacity; this was never attained in the field even after rain simulation. Higher NO emissions were measured in the lab in soil from burned plots at both 10% and 50% of maximum soil water holding capacity. Increasing the incubation temperature from 25 °C to 37 °C negatively affected microbial growth, mineralization and nitrification activities but enhanced N2O and CO2 production. Results indicate that fire did not increase post-burning soil GHG emissions in this tropical grasslands characterized by acidic, well drained and nutrient-poor soil.

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

Science.gov (United States)

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

2014-12-01

Understanding cultivar effects on field greenhouse gas (GHG) emissions in rice (Oryza sativa L.) systems is needed to improve the accuracy of predictive models used for estimating GHG emissions, and to determine to what extent choice of cultivar may have on GHG mitigation. We compared CH4 and N2O emissions, global warming potential (GWP = N2O + CH4), yield-scaled GWP (GWPY = GWP Mg-1 grain), and plant growth characteristics of 8 cultivars within 4 study sites in California and Arkansas. Seasonal CH4 emissions differed between cultivars by a factor of 2.1 and 1.3 at one California and one Arkansas site, respectively. Nitrous oxide emissions were negligible, comprised food security.

Redução da emissão de CO2, CH4 e H2S através da compostagem de dejetos suínos Reduction emissions of CO2, CH4 and H2S through composting of swine manure

Directory of Open Access Journals (Sweden)

Luana G. Sardá

2010-09-01

Full Text Available Em conjunto com o crescente desenvolvimento da tecnologia para a produção de suínos ocorreu uma forte exploração e degradação do ambiente, razão pela qual a atividade se transformou em fonte poluidora das regiões produtoras. Buscam-se, então, alternativas que minimizem o potencial poluidor do atual sistema de produção. O trabalho proposto foi comparar o perfil de emissão de dióxido de carbono (CO2, metano (CH4 e gás sulfídrico (H2S do manejo de dejetos suínos nas formas sólida (compostagem e líquida (esterqueira, e avaliar a eficiência do processo de compostagem através dos parâmetros físico-químicos. O ensaio foi implantado no campo experimental da EMBRAPA Suínos e Aves, localizada no município de Concórdia, SC. Contatou-se, na compostagem, uma redução de 7 vezes na emissão de CH4, com relação à esterqueira; a emissão de CO2 representou 78,5% do carbono total mineralizado. Considerando-se que a emissão de H2S foi expressiva apenas no manejo dos dejetos na forma líquida, pode-se afirmar que o manejo dos resíduos na forma sólida é uma alternativa para a redução dos impactos ambientais pela mitigação do efeito estufa e pela redução de odores.In conjunction with the development of technologies for the production of swine meat, a strong exploration and degradation of the environment occurred and the activity became a source of pollution in the producing regions. Therefore, there is a need for alternative technologies that minimize the pollutant potential of the current system of production. The proposed work was to analyze and to compare the emission of carbon dioxide (CO2, methane (CH4 and hydrogen sulfide (H2S between the management of swine manure in solid form (composting and liquid manure (deep pit, and assess the efficiency of the process of composting through the physical and chemical parameters. The test was implemented in the experimental field of Embrapa Suínos e Aves, located in Concordia (SC

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”...

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.

CO{sub 2} reforming of CH{sub 4} over stabilized mesoporous Ni-CaO-ZrO{sub 2} composites

Energy Technology Data Exchange (ETDEWEB)

Shuigang Liu; Lianxiu Guan; Junping Li; Ning Zhao; Wei Wei; Yuhan Sun [Chinese Academy of Sciences, Taiyuan (China). State Key Laboratory of Coal Conversion

2008-09-15

Mesoporous Ni-CaO-ZrO{sub 2} nanocomposites with high thermal stability were designed and employed in the CO{sub 2}/CH{sub 4} reforming. The nanocomposites with appropriate Ni/Ca/Zr molar ratios exhibited excellent activity and prominent coking resistivity. The Ni crystallites were effectively controlled under the critical size for coke formation in such nanocomposites. It was found that low Ni content resulted in high metal dispersion and good catalytic performance. Moreover, the basicity of the matrices improved the chemisorption of CO{sub 2} and promoted the gasification of deposited coke on the catalyst. 33 refs., 5 figs., 1 tab.

Fluxes of greenhouse gases CH{sub 4}, CO{sub 2} and N{sub 2}O on some peat mining areas in Finland

Energy Technology Data Exchange (ETDEWEB)

Nykaenen, H; Martikainen, P J [National Public Health Inst., Kuopio (Finland). Dept. of Biology; Silvola, J; Alm, J [Joensuu Univ. (Finland). Dept. of Biology

1997-12-31

The increase in concentration of greenhouse gases (CO{sub 2}, CH{sub 4} and N{sub 2}O) in atmosphere is associated with burning of fossil fuels and also changes in biogeochemistry due to land use activities. Virgin peatlands are globally important stores of carbon and sources of CH4. Peatland drainage changes the processes in carbon and nitrogen cycles responsible for the fluxes of CO{sub 2}, CH{sub 4} and N{sub 2}O. Preparing of peatlands for peat mining greatly change their biogeochemical processes. Effective drainage decreases water table and allows air to penetrate deep into peat profile. Aerobic conditions inhibit activities of anaerobic microbes, including the methanogens, whereas aerobic processes like methane oxidation are stimulated. Destruction of vegetation cover stops the carbon input to peat. In Finland the actual peat mining area is 0.05 x 106 hectares and further 0.03 x 106 hectares have been prepared or are under preparation for peat mining. The current total peatland area in the world used for mining is 0.94 x 106 ha and the area already mined is 1.15 x 106 ha. In this presentation fluxes of greenhouse gases (CH{sub 4}, CO{sub 2} and N{sub 2}O) on some mires under peat mining are reported and compared with those on natural mires and with the emissions from peat combustion. (15 refs.)

Fluxes of greenhouse gases CH{sub 4}, CO{sub 2} and N{sub 2}O on some peat mining areas in Finland

Energy Technology Data Exchange (ETDEWEB)

Nykaenen, H.; Martikainen, P.J. [National Public Health Inst., Kuopio (Finland). Dept. of Biology; Silvola, J.; Alm, J. [Joensuu Univ. (Finland). Dept. of Biology

1996-12-31

The increase in concentration of greenhouse gases (CO{sub 2}, CH{sub 4} and N{sub 2}O) in atmosphere is associated with burning of fossil fuels and also changes in biogeochemistry due to land use activities. Virgin peatlands are globally important stores of carbon and sources of CH4. Peatland drainage changes the processes in carbon and nitrogen cycles responsible for the fluxes of CO{sub 2}, CH{sub 4} and N{sub 2}O. Preparing of peatlands for peat mining greatly change their biogeochemical processes. Effective drainage decreases water table and allows air to penetrate deep into peat profile. Aerobic conditions inhibit activities of anaerobic microbes, including the methanogens, whereas aerobic processes like methane oxidation are stimulated. Destruction of vegetation cover stops the carbon input to peat. In Finland the actual peat mining area is 0.05 x 106 hectares and further 0.03 x 106 hectares have been prepared or are under preparation for peat mining. The current total peatland area in the world used for mining is 0.94 x 106 ha and the area already mined is 1.15 x 106 ha. In this presentation fluxes of greenhouse gases (CH{sub 4}, CO{sub 2} and N{sub 2}O) on some mires under peat mining are reported and compared with those on natural mires and with the emissions from peat combustion. (15 refs.)

Carbon nanosheets by microwave plasma enhanced chemical vapor deposition in CH4-Ar system

International Nuclear Information System (INIS)

Wang Zhipeng; Shoji, Mao; Ogata, Hironori

2011-01-01

We employ a new gas mixture of CH 4 -Ar to fabricate carbon nanosheets by microwave plasma enhanced chemical vapor deposition at the growth temperature of less than 500 deg. C. The catalyst-free nanosheets possess flower-like structures with a large amount of sharp edges, which consist of a few layers of graphene sheets according to the observation by transmission electron microscopy. These high-quality carbon nanosheets demonstrated a faster electron transfer between the electrolyte and the nanosheet surface, due to their edge defects and graphene structures.

AR coating with high damage threshold on SiO2 glass. Final report

International Nuclear Information System (INIS)

Toratani, H.; Kanamori, C.; Nakajima, S.; Nakagawa, K.; Izumitani, T.

1983-01-01

The following experimental results are shown: (1) uniformity of AR coatings on Optosil and Sprasil provided by LLNL; (2) relation between cleaning methods and properties of AR coatings; (3) baking and sintering conditions of gel-derived films; (4) heat treatment of AR coating in O 2 flow

AES, EELS and XPS characterization of Ti(C, N, O) films prepared by PLD using a Ti target in N2, CH4, O2 and CO as reactive gases

International Nuclear Information System (INIS)

Soto, G.

2004-01-01

Titanium-based films were grown on (1 0 0)-Si substrates by the pulsed laser deposition (PLD) method using a Ti target in reactive atmospheres. The films were grown in vacuum (Ti-film), O 2 (TiO x ), N 2 (TiN x ), CH 4 (TiC x ), CO (TiC x O y ), N 2 +CH 4 (TiC x N y ) and CO+N 2 (TiC x N y O z ). After depositions, every film is characterized in situ by Auger, electron-energy loss and X-ray photoelectron (XPS) spectroscopies. For the binary compounds the stoichiometry is regulated without difficulty by gas pressure during ablation. However, for ternary and quaternary compounds there is a tendency to produce chemically inhomogeneous films. For example, the ablation of Ti in a N 2 +CH 4 environment results in a TiNC:C composite. In this case, the overabundance of nitrogen influences the segregation of carbon. In the other hand, the O 2 +CH 4 mixture was ineffectively to produce TiC x O y films, yielding mostly TiO 2 with traces of embedded carbon. By using CO as reactive gas the TiC x O y films were completed. Also, a mixture of CO with N 2 was tested to produce quaternary TiC x N y O z compounds. Based on these results, it is recommended that better control on film stoichiometry and chemical homogeneity can be achieved by using reactive gases with predetermined C:N:O ratios

Hybrid model of atmospheric pressure Ar/O{sub 2}/TiCl{sub 4} radio-frequency capacitive discharge for TiO{sub 2} deposition

Energy Technology Data Exchange (ETDEWEB)

Leblanc, A. [ENS Cachan, UPMC, Paris (France); Ding, Ke [College of Science, Donghua University, Shanghai 201620 (China); Lieberman, M. A., E-mail: lieber@eecs.berkeley.edu [Department of Electrical Engineering, University of California, Berkeley, California 94720 (United States); Wang, De Xin; Zhang, Jing; Jun Shi, Jian [College of Materials Science and Engineering, Donghua University, Shanghai 201620 (China)

2014-05-14

A hybrid global-analytical model of an atmospheric pressure radio-frequency driven capacitive discharge is applied to determine the plasma conditions for TiO{sub 2} film deposition. The feed gas is mainly argon with a small fraction of O{sub 2} and a smaller fraction of TiCl{sub 4}. Variations of the discharge parameters and species densities with O{sub 2} concentration, discharge power, and flow rate are determined. A simplified chemistry model is developed and compared with the simulation results, showing good agreement. For a base case with Ar/O{sub 2}/TiCl{sub 4} flow rates of 203/30/0.17 sccm, the results indicate that a minimum O{sub 2} fraction of 7.3 × 10{sup −4} is required for pure (un-chlorinated) TiO{sub 2} film deposition that the active precursor species is TiO{sub 2}Cl{sub 3}, with subsequent abstraction of Cl atoms by dissociative electron attachment and that the deposition rates are around 1 nm/s.

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions: Quarterly Report.

Energy Technology Data Exchange (ETDEWEB)

Wang, Yifeng [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-11-01

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO₂ and H₂O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH₄) during hydrofracturing and gas extraction. Note that liquid or supercritical CO₂ has been suggested as an alternative fluid for subsurface fracturing such that CO₂ enhanced gas recovery can also serve as a CO₂ sequestration process. Limited data indicate that CO₂ may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH₄ in shale. Similarly, the presence of water moisture seems able to displace or trap CH₄ in shale matrix. Therefore, fundamental understanding of CH₄-CO₂-H₂O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO₂ sequestration. This project focuses on the systematic study of CH₄-CO₂-H₂O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

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

OpenAIRE

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

2016-01-01

Using a comprehensive data set (dissolved CH4, ?13C-CH4, ?2H-CH4, ?13C-DIC, ?37Cl, ?2H-H2O, ?18O-H2O, Na, K, Ca, Mg, HCO3, Cl, Br, SO4, NO3 and DO), in combination with a novel application of isometric log ratios, this study describes hydrochemical and thermodynamic controls on dissolved CH4 from a coal seam gas reservoir and an alluvial aquifer in the Condamine catchment, eastern Surat/north-western Clarence-Moreton basins, Australia. ?13C-CH4 data in the gas reservoir (?58? to ?49?) and sha...

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

NARCIS (Netherlands)

van Essen, Vincent; Sepman, Alexey; Mokhov, A. V.; Levinsky, H. B.

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH4/O-2/N-2 flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The

Growing season CH4 and N2O fluxes from a subarctic landscape in northern Finland; from chamber to landscape scale

Science.gov (United States)

Dinsmore, Kerry J.; Drewer, Julia; Levy, Peter E.; George, Charles; Lohila, Annalea; Aurela, Mika; Skiba, Ute M.

2017-02-01

Subarctic and boreal emissions of CH4 are important contributors to the atmospheric greenhouse gas (GHG) balance and subsequently the global radiative forcing. Whilst N2O emissions may be lower, the much greater radiative forcing they produce justifies their inclusion in GHG studies. In addition to the quantification of flux magnitude, it is essential that we understand the drivers of emissions to be able to accurately predict climate-driven changes and potential feedback mechanisms. Hence this study aims to increase our understanding of what drives fluxes of CH4 and N2O in a subarctic forest/wetland landscape during peak summer conditions and into the shoulder season, exploring both spatial and temporal variability, and uses satellite-derived spectral data to extrapolate from chamber-scale fluxes to a 2 km × 2 km landscape area.From static chamber measurements made during summer and autumn campaigns in 2012 in the Sodankylä region of northern Finland, we concluded that wetlands represent a significant source of CH4 (3.35 ± 0.44 mg C m-2 h-1 during the summer campaign and 0.62 ± 0.09 mg C m-2 h-1 during the autumn campaign), whilst the surrounding forests represent a small sink (-0.06 ± zero across both ecosystems.We found a weak negative relationship between CH4 emissions and water table depth in the wetland, with emissions decreasing as the water table approached and flooded the soil surface and a positive relationship between CH4 emissions and the presence of Sphagnum mosses. Temperature was also an important driver of CH4 with emissions increasing to a peak at approximately 12 °C. Little could be determined about the drivers of N2O emissions given the small magnitude of the fluxes.A multiple regression modelling approach was used to describe CH4 emissions based on spectral data from PLEIADES PA1 satellite imagery across a 2 km × 2 km landscape. When applied across the whole image domain we calculated a CH4 source of 2.05 ± 0.61 mg C m-2 h-1. This was

Smooth YBa2Cu3O7-x thin films prepared by pulsed laser deposition in O2/Ar atmosphere

DEFF Research Database (Denmark)

Kyhle, Anders; Skov, Johannes; Hjorth, Søren

1994-01-01

We report on pulsed laser deposition of YBa2Cu3O7-x in a diluted O2/Ar gas resulting in thin epitaxial films which are almost outgrowth-free. Films were deposited on SrTiO3 or MgO substrates around 800-degrees-C at a total chamber pressure of 1.0 mbar, varying the argon partial pressure from 0 to 0.......6 mbar. The density of boulders and outgrowths usual for laser deposited films varies strongly with Ar pressure: the outgrowth density is reduced from 1.4 x 10(7) to 4.5 x 10(5) cm-2 with increasing Ar partial pressure, maintaining a critical temperature T(c,zero) almost-equal-to 90 K and a transport...... critical current density J(c)(77 K) greater-than-or-equal-to 10(6) A/cm2 by extended oxygenation time during cool down....

Annual balances of CH4 and N2O from a managed fen meadow using eddy covariance flux measurements

International Nuclear Information System (INIS)

Schrier-Uijl, A.P.; Veenendaal, E.M.; Kroon, P.S.; Hensen, A.; Jonker, H.J.J.

2010-10-01

Annual terrestrial balances of methane (CH4) and nitrous oxide (N2O) are presented for a managed fen meadow in the Netherlands for 2006, 2007 and 2008, using eddy covariance (EC) flux measurements. Annual emissions derived from different methods are compared. The most accurate annual CH4 flux is achieved by gap filling EC fluxes with an empirical multivariate regression model, with soil temperature and mean wind velocity as driving variables. This model explains about 60% of the variability in observed daily CH4 fluxes. Annual N2O emissions can be separated into background emissions and event emissions due to fertilization. The background emission is estimated using a multivariate regression model also based on EC flux data, with soil temperature and mean wind velocity as driving variables. The event emissions are estimated using emission factors. The minimum direct emission factor is derived for six fertilization events by subtracting the background emission, and the IPCC default emission factor of 1% is used for the other events. In addition, the maximum direct emission factors are determined for the six events without subtracting the background emission. The average direct emission factor ranges from 1.2 to 2.8%, which is larger than the IPCC default value. Finally, the total terrestrial greenhouse gas balance is estimated at 16 Mg ha -1 year -1 in CO2-equivalents with contributions of 30, 25 and 45% by CO2, CH4 and N2O, respectively.

Improvement in ferroelectric properties of Pt/PZT/Pt capacitors etched as a function of Ar/O2 gas mixing ratio into Cl2/CF4 plasma

International Nuclear Information System (INIS)

Lim, Kyu-Tae; Koo, Seong-Mo; Kim, Kyoung-Tae; Kim, Dong-Pyo; Kim, Chang-Il

2004-01-01

In this work, to investigate improvement of the damage using oxygen containing plasma, we etched PZT films as a function of Ar (x%)/O 2 (y%) gas mixing ratio in Cl 2 (56%)/CF 4 (14%) plasma (where the sum of x and y is 30). The maximum etch rate of the PZT thin films was 146 nm/min for Ar (30%)/O 2 (0%) added into the Cl 2 /CF 4 plasma. After the etching, the plasma-induced damages were characterized in terms of hysteresis curves, leakage current, switching polarization and retention capacity as a function of the gas mixing ratio. When the ferroelectric properties of PZT films were etched as a function of O 2 and Ar and the gas mixing ratios were compared, the value of remnant polarization in O 2 (30%) added Cl 2 /CF 4 plasma is higher than that in Ar (30%). The results showed that after the etching the charges accumulated by oxygen vacancies prevented further domain switching at the top electrode-ferroelectric interface and created leakage current because of modification of the interfacial Schottky barrier during the etching process. The physical damage to the near surface and the crystal structure of the etched PZT thin films was evaluated by using X-ray diffraction (XRD). The remnant polarization, leakage current, retention and fatigue properties are improved with increasing O 2 content. From XRD results, the improvement in the ferroelectric properties of PZT capacitors etched in O 2 containing plasma was consistent with the increased intensities of the (100) and (200) peaks

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.

Impact of the heatwave in 2003 on the summer CH4 and N2O budget of a spruce forest ecosystem: A four-year comparison

Science.gov (United States)

Lamers, M.; Fiedler, S.; Jungkunst, H. F.; Stahr, K.; Streck, T.

2009-04-01

Both CH4 and N2O reduction and oxidation are highly sensitive to variation in soil moisture. Significant changes of net CH4 and total N2O fluxes from soils can therefore be expected to accompany redistribution for precipitation in the course of climate change where more extreme events are predicted for the future. The extreme summer drought in 2003 offered the unique opportunity to study the impact of such events on the emission of greenhouse gases, such as methane or nitrous oxide, under field conditions. The main objective of the present study was to evaluate the impact of the summer drought in 2003 on the net methane and nitrous oxide budget of a spruce forest ecosystem (South-West Germany) with large variation in soil drainage. During the summers of 2000-2004 we measured net CH4 and N2O fluxes (bi)-weekly using the closed-chamber technique for six different soil types ranging from well-aerated Cambisols to poorly drained Gleysols and a wet Histosol. With regard to CH4 the extreme summer draught (1) did not elevate net CH4-sink function of soils, but (2) highly reduced net CH4-source strength and (3) reversed the net CH4 source of the investigated catchment into a sink. In all four summers investigated, net ecosystem exchange of CH4 was found only in the hydromorphic soils but not in the dominant well-aerated soils. This highlighted the key role of hydromorphic soils for the investigated pedodiverse system. With regard to N2O the summer draught in 2003 significantly reduced N2O emissions at least for the Humic Gleysol and the Sapric Histosol and hence markedly reduced the net N2O source strength of the investigated ecosystem.

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

Science.gov (United States)

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

2015-04-01

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

Distribution of dissolved green-house gases (CO2, CH4, N2O) in Lakes Edward and George: Results from the first field cruise of the HIPE project

Science.gov (United States)

Borges, Alberto V.; Morana, Cédric D. T.; Lambert, Thibault; Okello, William; Bouillon, Steven

2017-04-01

Inland waters (streams, rivers, lakes, reservoirs) are quantitatively important components of the global budgets of atmospheric emissions of long-lived greenhouse gases (GHGs) (CO2, CH4, N2O). Available data indicate that a very large fraction of CO2 and CH4 emissions from rivers and reservoirs occurs at tropical latitudes. Data on GHGs at tropical latitudes from lakes however are much more scarse, and the relative importance of emissions, in particular in Africa, remains to be determined. Large tropical lakes are net autotrophic (hence potentially sinks for atmospheric CO2) due generally low dissolved organic carbon concentrations, seasonally near constant light and temperature conditions, and generally deep water columns favourable for export of organic matter to depth. This sharply contrasts with their much better documented temperate and boreal counterparts, usually considered as CO2 sources to the atmosphere sustained by net heterotrophy. Here, we report a data-set of dissolved CO2, CH4, N2O obtained in October 2016 in Lakes Edward and George and adjacent streams and crater lakes in the frame of Belgian Science Policy (BELSPO) HIPE (Human impacts on ecosystem health and resources of Lake Edward, http://www.co2.ulg.ac.be/hipe/) project. Lake George and part of Lake Edward were sinks for atmospheric CO2 and N2O due to high primary production and denitrification in sediments, respectively, and modest sources of CH4 to the atmosphere. Sampled rivers and streams were oversaturated in CO2 and CH4 and close to atmospheric equilibrium with regards to N2O. Spatial variations within rivers and streams were related to elevation and vegetation characteristics on the catchments (savannah versus forest). Levels of CO2, CH4, and N2O were within the range of those we reported in other African rivers. Crater lakes acted as sinks for atmospheric CO2 and N2O but were extremely over-saturated in CH4, due to intense primary production sustained by cyanobacteria. These CH4 levels

Application of biochar and nitrogen influences fluxes of CO2, CH4 and N2O in a forest soil.

Science.gov (United States)

Hawthorne, Iain; Johnson, Mark S; Jassal, Rachhpal S; Black, T Andrew; Grant, Nicholas J; Smukler, Sean M

2017-05-01

Nitrogen (N) fertilization of forests for increasing carbon sequestration and wood volume is expected to influence soil greenhouse gas (GHG) emissions, especially to increase N 2 O emissions. As biochar application is known to affect soil GHG emissions, we investigated the effect of biochar application, with and without N fertilization, to a forest soil on GHG emissions in a controlled laboratory study. We found that biochar application at high (10%) application rates increased CO 2 and N 2 O emissions when applied without urea-N fertilizer. At both low (1%) and high biochar (10%) application rates CH 4 consumption was reduced when applied without urea-N fertilizer. Biochar application with urea-N fertilization did not increase CO 2 emissions compared to biochar amended soil without fertilizer. In terms of CO 2 -eq, the net change in GHG emissions was mainly controlled by CO 2 emissions, regardless of treatment, with CH 4 and N 2 O together accounting for less than 1.5% of the total emissions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Substituent effect in spin-crossover behavior of iron(II)-Ar-pybox complexes (Ar-pybox = 4-aryl-2,6-bis(oxazolin-2-yl)pyridine)

Science.gov (United States)

Kimura, Akifumi; Ishida, Takayuki

2018-01-01

Spin-crossover (SCO) is a reversible transition between low-spin (LS) and high-spin (HS) states by external stimuli like heat. The SCO behavior of [Fe(Ar-pybox)2](ClO4)2 was investigated, where Ar-pybox stands for 4-aryl-2,6-bis(oxazolin-2-yl)pyridine with Ar = 4-pyridyl (4Py), 3-thienyl (3Th), and phenyl (Ph). They were characterized by means of single-crystal X-ray diffraction study, being consistent with the results of the magnetic measurements. The SCO temperatures (T1/2) in the polycrystalline state were determined to be 360 and 230 K for Ar = 4Py and Ph, respectively. The 3Th derivative possessed a HS state in all the temperature range. The solution susceptometry was also performed to purge intermolecular interaction and rigid crystal lattice effects, affording T1/2 = 310, 240, and 240 K for Ar = 4Py, 3Th, and Ph, respectively, in acetone. The substituent effect analysis using the Hammett substituent constant (σp) clarified that electron-withdrawing groups raise T1/2. A plausible model describing the substituent effect on T1/2 is proposed based on d-π interaction. The present result is regarded as a successful example of crystal field engineering.

Anthropogenic effects on greenhouse gas (CH4 and N2O) emissions in the Guadalete River Estuary (SW Spain)

International Nuclear Information System (INIS)

Burgos, M.; Sierra, A.; Ortega, T.; Forja, J.M.

2015-01-01

Coastal areas are subject to a great anthropogenic pressure because more than half of the world's population lives in its vicinity causing organic matter inputs, which intensifies greenhouse gas emissions into the atmosphere. Dissolved concentrations of CH 4 and N 2 O have been measured seasonally during 2013 in the Guadalete River Estuary, which flows into the Cadiz Bay (southwestern Spanish coast). It has been intensely contaminated since 1970. Currently it receives wastewater effluents from cities and direct discharges from nearby agriculture crop. Eight sampling stations have been established along 18 km of the estuary. CH 4 and N 2 O were measured using a gas chromatograph connected to an equilibration system. Additional parameters such as organic matter, dissolved oxygen, nutrients and chlorophyll were determinate as well, in order to understand the relationship between physicochemical and biological processes. Gas concentrations increased from the River mouth toward the inner part, closer to the wastewater treatment plant discharge. Values varied widely within 21.8 and 3483.4 nM for CH 4 and between 9.7 and 147.6 nM for N 2 O. Greenhouse gas seasonal variations were large influenced by the precipitation regime, masking the temperature influence. The Guadatete Estuary acted as a greenhouse gas source along the year, with mean fluxes of 495.7 μmol m −2 d −1 and 92.8 μmol m −2 d −1 for CH 4 and N 2 O, respectively. - Highlights: • The estuary acts as a source of atmospheric methane and nitrous oxide. • Anthropogenic inputs affect the distribution of the greenhouse gases. • Dissolved gases presented an important longitudinal gradient. • Seasonal variations highly depended on the precipitation regimen

Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported Ni and Co Catalysts: Full Factorial Design Screening

Directory of Open Access Journals (Sweden)

M. Anwar Hossain

2018-01-01

Full Text Available In this study, the potential of dry reforming reaction over CaFe2O4 supported Ni and Co catalysts were investigated. The Co/CaFe2O4 and Ni/CaFe2O4 catalysts were synthesized using wet impregnation method by varying the metal loading from 5-15 %. The synthesized catalysts were tested in methane dry reforming reaction at atmospheric pressure and reaction temperature ranged 700-800 oC. The catalytic performance of the catalysts based on the initial screening is ranked as 5%Co/CaFe2O4 < 10%Co/CaFe2O4 < 5%Ni/CaFe2O4 < 10%Ni/CaFe2O4 according to their performance. The Ni/CaFe2O4 catalyst was selected for further investigation using full factorial design of experiment. The interaction effects of three factors namely metal loading (5-15 %, feed ratio (0.4-1.0, and reaction temperature (700-800 oC were evaluated on the catalytic activity in terms of CH4 and CO2 conversion as well as H2 and CO yield. The interaction between the factors showed significant effects on the catalyst performance at metal loading, feed ratio and reaction temperature of 15 %, 1.0, and 800 oC. respectively. The 15 wt% Ni/CaFe2O4 was subsequently characterized by Thermogravimetric (TGA, X-ray Diffraction (XRD, Field Emission Scanning Electron Microscopy (FESEM, Energy Dispersive X-ray Spectroscopy (EDX, X-ray Photoelectron Spectroscopy (XPS, N2-physisorption, Temperature Programmed Desorption (TPD-NH3, TPD-CO2, and Fourier Transform Infra Red (FTIR to ascertain its physiochemical properties.  This study demonstrated that the CaFe2O4 supported Ni catalyst has a good potential to be used for syngas production via methane dry reforming. Copyright © 2018 BCREC Group. All rights reserved Received: 5th May 2017; Revised: 8th August 2017; Accepted: 9th August 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Hossain, M.A., Ayodele, B.V., Cheng, C.K., Khan, M.R. (2018. Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported

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

Science.gov (United States)

Dimitrov, D. D.; Wang, J.

2016-12-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan [College of Resources and Environmental Sciences, Agricultural University of Hebei, 071000 Baoding (China); Gao, Zhiling, E-mail: zhilinggao@hotmail.com [College of Resources and Environmental Sciences, Agricultural University of Hebei, 071000 Baoding (China); Ma, Wenqi; Wang, Dianwu [College of Resources and Environmental Sciences, Agricultural University of Hebei, 071000 Baoding (China); Cao, Yufeng; Li, Jianguo [College of Animal Science and Technology, Agricultural University of Hebei, 071000 Baoding (China); Cai, Zhenjiang [Mechanical and Electric Engineering College, Agricultural University of Hebei, 071000 Baoding (China)

2015-04-15

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

Detonation study of two stoichiometric mixtures (CH{sub 4}/H{sub 2}/O{sub 2}/N{sub 2} and CH{sub 4}/C{sub 2}H{sub 6}/O{sub 2}/N{sub 2}). Influence of the relative proportion of both fuels and of the initially high temperature; Etude de la detonation de deux melanges stoechiometriques (CH{sub 4}/H{sub 2}/O{sub 2}/N{sub 2} et CH{sub 4}/C{sub 2}H{sub 6}/O{sub 2}/N{sub 2}). Influence de la proportion relative des deux combustibles et de la temperature initiale elevee

Energy Technology Data Exchange (ETDEWEB)

Matignon, Ch.

2000-12-15

Detonations of gaseous reactive mixtures made of two fuels of very different detonability xH{sub 2}+(1-x)CH{sub 4} and xC{sub 2}H{sub 6}+(1-x)CH{sub 4} in stoichiometric proportion with oxygen and diluted with nitrogen (in proportions varying from pure oxygen to the air) are investigated. The parameters of the study are the relative proportion x of fuels, nitrogen dilution B = O{sub 2}/N{sub 2} and the initial conditions of temperature and pressure. This study takes place within the general context of the chemical process safety improvement. Detonability was evaluated by the comparison between the characteristic cell size measurement of the three-dimensional structure of the autonomous and stationary detonation front with the chemical induction length calculated on the assumptions of the ZND model by means of several detailed chemical kinetics mechanisms. The results obtained for the mixtures with single fuel show that the detonability of methane decreases according to the initial temperature whatever the dilution B, and that the one of ethane and hydrogen decreases with B = 0 but increases with B = 3,76 (air) (the inversion of behaviour occurs for B = 2 for ethane, and B=1 for hydrogen). The results obtained for the mixtures with two fuels show that their detonability is each time influenced by the heaviest fuel, i.e. that the detonability of H{sub 2}/CH{sub 4} mixtures is rather controlled by CH{sub 4} whereas the one of C{sub 2}H{sub 6}/CH{sub 4} mixtures is rather controlled by C{sub 2}H{sub 6}. With pure oxygen (B = 0), these mixtures are desensitized by the increase of the initial temperature. Beyond a certain value x, an inversion of detonability according to x is observed. (author)

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.

Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices

International Nuclear Information System (INIS)

Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

2012-01-01

Irradiation at 239 ± 20 nm of a p-H 2 matrix containing methoxysulfinyl chloride, CH 3 OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν 1 , CH 2 antisymmetric stretching), 2999.5 (ν 2 , CH 3 antisymmetric stretching), 2950.4 (ν 3 , CH 3 symmetric stretching), 1465.2 (ν 4 , CH 2 scissoring), 1452.0 (ν 5 , CH 3 deformation), 1417.8 (ν 6 , CH 3 umbrella), 1165.2 (ν 7 , CH 3 wagging), 1152.1 (ν 8 , S=O stretching mixed with CH 3 rocking), 1147.8 (ν 9 , S=O stretching mixed with CH 3 wagging), 989.7 (ν 10 , C-O stretching), and 714.5 cm -1 (ν 11 , S-O stretching) modes of syn-CH 3 OSO. When CD 3 OS(O)Cl in a p-H 2 matrix was used, lines at 2275.9 (ν 1 ), 2251.9 (ν 2 ), 2083.3 (ν 3 ), 1070.3 (ν 4 ), 1056.0 (ν 5 ), 1085.5 (ν 6 ), 1159.7 (ν 7 ), 920.1 (ν 8 ), 889.0 (ν 9 ), 976.9 (ν 10 ), and 688.9 (ν 11 ) cm -1 appeared and are assigned to syn-CD 3 OSO; the mode numbers correspond to those used for syn-CH 3 OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86/aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH 3 OSO near 2991, 2956, 1152, and 994 cm -1 to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD 3 OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H 2 such that the Cl atom, produced via UV photodissociation of CH 3 OS(O)Cl in situ, might escape from the original cage to yield isolated CH 3 OSO radicals.

Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices.

Science.gov (United States)

Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

2012-03-28

Irradiation at 239 ± 20 nm of a p-H(2) matrix containing methoxysulfinyl chloride, CH(3)OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν(1), CH(2) antisymmetric stretching), 2999.5 (ν(2), CH(3) antisymmetric stretching), 2950.4 (ν(3), CH(3) symmetric stretching), 1465.2 (ν(4), CH(2) scissoring), 1452.0 (ν(5), CH(3) deformation), 1417.8 (ν(6), CH(3) umbrella), 1165.2 (ν(7), CH(3) wagging), 1152.1 (ν(8), S=O stretching mixed with CH(3) rocking), 1147.8 (ν(9), S=O stretching mixed with CH(3) wagging), 989.7 (ν(10), C-O stretching), and 714.5 cm(-1) (ν(11), S-O stretching) modes of syn-CH(3)OSO. When CD(3)OS(O)Cl in a p-H(2) matrix was used, lines at 2275.9 (ν(1)), 2251.9 (ν(2)), 2083.3 (ν(3)), 1070.3 (ν(4)), 1056.0 (ν(5)), 1085.5 (ν(6)), 1159.7 (ν(7)), 920.1 (ν(8)), 889.0 (ν(9)), 976.9 (ν(10)), and 688.9 (ν(11)) cm(-1) appeared and are assigned to syn-CD(3)OSO; the mode numbers correspond to those used for syn-CH(3)OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86∕aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH(3)OSO near 2991, 2956, 1152, and 994 cm(-1) to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD(3)OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H(2) such that the Cl atom, produced via UV photodissociation of CH(3)OS(O)Cl in situ, might escape from the original cage to yield isolated CH(3)OSO radicals.

Emissions of CH4, N2O, NH3 and odorants from pig slurry during winter and summer storage

DEFF Research Database (Denmark)

Petersen, Søren O; Dorno, Nadia; Lindholst, Sabine

2013-01-01

to the water balance of the surface crust. An N2O emission factor for slurry storage with a straw crust was estimated at 0.002–0.004. There was no evidence for a reduction of CH4 emissions with a crust. Current Intergovernmental Panel on Climate Change recommendations for N2O and CH4 emission factors....... Pig slurry was stored with or without a straw crust, and with or without interception of precipitation, i.e., four treatments, in two randomized blocks. Emissions of total reduced S (mainly H2S) and p-cresol, but not skatole, were reduced by the straw crust. Total GHG emissions were 0.01–0.02 kg CO2...

Structural study of CH4, CO2 and H2O clusters containing from several tens to several thousands of molecules

Science.gov (United States)

Torchet, G.; Farges, J.; de Feraudy, M. F.; Raoult, B.

Clusters are produced during the free jet expansion of gaseous CH4, CO2 or H2O. For a given stagnation temperature To, the mean cluster size is easily increased by increasing the stagnation pressure p0. On the other hand, the cluster temperature does not depend on stagnation conditions but mainly on properties of the condensed gas. An electron diffraction analysis provides information about the cluster structure. Depending on whether the diffraction patterns exhibit crystalline lines or not, the structure is worked out either by using crystallographic methods or by constructing cluster models. When they contain more than a few thousand molecules, clusters show a crystalline structure identical to that of one phase, namely, the cubic phase, known in bulk solid: plastic phase (CH4), unique solid phase (CO2) or metastable cubic phase (H2O). When decreasing the cluster size, the studied compounds behave quite differently: CO2 clusters keep the same crystalline structure, CH4 clusters show the multilayer icosahedral structure wich has been found in rare gas clusters, and H2O clusters adopt a disordered structure different from the amorphous structures of bulk ice. Des agrégats sont produits au cours de la détente en jet libre des gaz CH4, CO2 ou H2O. Pour une température initiale donnée To, on accroît facilement la taille moyenne des agrégats en augmentant la pression initiale po . Par contre, la température des agrégats dépend principalement des propriétés du gaz condensé. Une analyse par diffraction électronique permet l'étude de la structure des agrégats. Selon que les diagrammes de diffraction contiennent ou non des raies cristallines, on a recours soit à des méthodes cristallographiques soit à la construction de modèles d'agrégats. Lorsqu'ils renferment plus de quelques milliers de molécules, les agrégats adoptent la structure cristalline de l'une des phases connues du solide massif et plus précisément la phase cubique : phase plastique pour

Rotational energy transfer in Na2 (A Σ) colliding with Xe, Kr, Ar, Ne, He, H2, CH4, and N2: Experiment and fitting laws

International Nuclear Information System (INIS)

Brunner, T.A.; Smith, N.; Karp, A.W.; Pritchard, D.E.

1981-01-01

Using the method of laser-induced fluorescence, we have measured level to level rate constants for rotational energy transfer (RET) in Na 2 colliding with Xe, Kr, Ar, Ne, He, H 2 , N 2 , and CH 4 . For each target gas we varied the initial rotational quantum number ji-italic over a wide range, typically 4--100, and measured approximately 60 rate constants with an average error of between 6% and 9%. The resulting base of 479 rate constants is used to test several recently proposed fitting laws. The energy corrected sudden scaling law of DePristo et al., when combined with the assumption of a power gap law for the basis rate constants k/sub l/→0, fit with only 3 parameters all of the data for a given target gas with 7%--12% average percentage deviation. Our statistical power gap law worked well and was generally the best law for those data sets with only one value of j/sub i/. The worst fits in all cases considered here were those using the exponential gap law of surprisal theory

Synthesis of flat sticky hydrophobic carbon diamond-like films using atmospheric pressure Ar/CH4 dielectric barrier discharge

Science.gov (United States)

Rincón, R.; Hendaoui, A.; de Matos, J.; Chaker, M.

2016-06-01

An Ar/CH4 atmospheric pressure dielectric barrier discharge (AP-DBD) was used to synthesize sticky hydrophobic diamond-like carbon (DLC) films on glass surface. The film is formed with plasma treatment duration shorter than 30 s, and water contact angles larger than 90° together with contact angle hysteresis larger than 10° can be achieved. According to Fourier transform infrared spectroscopy and atomic force microscopy analysis, hydrocarbon functional groups are created on the glass substrate, producing coatings with low surface energy (˜35 mJ m-2) with no modification of the surface roughness. To infer the plasma processes leading to the formation of low energy DLC surfaces, optical emission spectroscopy was used. From the results, a direct relationship between the CH species present in the plasma and the carbon concentration in the hydrophobic layer was found, which suggests that the CH species are the precursors of DLC film growth. Additionally, the plasma gas temperature was measured to be below 350 K which highlights the suitability of using AP-DBD to treat thermo-sensitive surfaces.

Periphery-palladated carbosilane dendrimers : Synthesis and reactivity of model organopalladium(II) and (IV) complexes : Crystal structure of [PdMe(C6H4(OCH2Ph)-4)(bpy)] (bpy=2,2'-bipyridine

NARCIS (Netherlands)

Koten, G. van; Hovestad, N.J.; Hoare, J.L.; Jastrzebski, J.T.B.H.; Canty, A.J.; Smeets, W.J.J.; Spek, A.L.

1999-01-01

A carbosilane dendrimer with 12 peripheral iodoarene groups, [Si{(CH2)3Si((CH2)3SiMe2(C6H4CH2OC6H4I-4))3}4] (G1-ArI, 9), and the corresponding G0 model compound [Si{(CH2)3SiMe2(C6H4CH2OC6H4I-4)}4] (G0-ArI, 8) have been prepared from [Si{(CH2)3Si((CH2)3SiMe2(C6H4CH2Br))3}4] (G1-Br, 7) and the

Soil CO2 CH4 and N2O fluxes from an afforested lowland raised peatbog in Scotland: implications for drainage and restoration

Directory of Open Access Journals (Sweden)

J. I. L. Morison

2013-02-01

Full Text Available The effect of tree (lodgepole pine planting with and without intensive drainage on soil greenhouse gas (GHG fluxes was assessed after 45 yr at a raised peatbog in West Flanders Moss, central Scotland. Fluxes of CO2 CH4 and N2O from the soil were monitored over a 2-yr period every 2 to 4 weeks using the static opaque chamber method in a randomised experimental block trial with the following treatments: drained and planted (DP, undrained and planted (uDP, undrained and unplanted (uDuP and for reference also from an adjoining near-pristine area of bog at East Flanders Moss (n-pris. There was a strong seasonal pattern in both CO2 and CH4 effluxes which were significantly higher in late spring and summer months because of warmer temperatures. Effluxes of N2O were low and no significant differences were observed between the treatments. Annual CH4 emissions increased with the proximity of the water table to the soil surface across treatments in the order: DP 4 m−2 yr−1, respectively. For CO2, effluxes increased in the order uDP 2 m−2 yr−1, respectively. CO2 effluxes dominated the total net GHG emission, calculated using the global warming potential (GWP of the three GHGs for each treatment (76–98%, and only in the n-pris site was CH4 a substantial contribution (23%. Based on soil effluxes only, the near pristine (n-pris peatbog had 43% higher total net GHG emission compared with the DP treatment because of high CH4 effluxes and the DP treatment had 33% higher total net emission compared with the uDP because drainage increased CO2 effluxes. Restoration is likely to increase CH4 emissions, but reduce CO2 effluxes. Our study suggests that if estimates of CO2 uptake by vegetation from similar peatbog sites were included, the total net GHG emission of restored peatbog would still be higher than that of the peatbog with trees.

One-Pot Synthesis of Cu-Nanocluster-Decorated Brookite TiO2 Quasi-Nanocubes for Enhanced Activity and Selectivity of CO2 Photoreduction to CH4.

Science.gov (United States)

Jin, Jingpeng; Luo, Jiang; Zan, Ling; Peng, Tianyou

2017-11-17

A new kind of metallic Cu-loaded brookite TiO 2 composite, in which Cu nanoclusters with a small size of 1-3 nm are decorated on brookite TiO 2 quasi nanocube (BTN) surfaces (hereafter referred to as Cu-BTN), is synthesized via a one-pot hydrothermal process and then used as photocatalyst for CO 2 reduction. It was found that the decoration of Cu nanoclusters on BTN surfaces can improve the activity and selectivity of CO 2 photoreduction to CH 4 , and 1.5 % Cu-BTN gives a maximum overall photocatalytic activity (150.9 μmol g -1  h -1 ) for CO/CH 4 production, which is ≈11.4 and ≈3.3 times higher than those of pristine BTN (13.2 μmol g -1  h -1 ) and Ag-BTN (45.2 μmol g -1  h -1 ). Moreover, the resultant Cu-BTN products can promote the selective generation of CH 4 as compared to CO due to the number of surface oxygen vacancies and the CO 2 /H 2 O adsorption behavior, which differs from that of the pristine BTN. The present results demonstrate that brookite TiO 2 would be a potential effective photocatalyst for CO 2 photoreduction, and that Cu nanoclusters can act as an inexpensive and efficient co-catalyst alternative to the commonly used noble metals to improve the photoactivity and selectivity for CO 2 reduction to CH 4 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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).

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.

Spatial and temporal patterns of CH4 and N2O fluxes in terrestrial ecosystems of North America during 1979–2008: application of a global biogeochemistry model

Directory of Open Access Journals (Sweden)

C. Lu

2010-09-01

Full Text Available Continental-scale estimations of terrestrial methane (CH4 and nitrous oxide (N2O fluxes over a long time period are crucial to accurately assess the global balance of greenhouse gases and enhance our understanding and prediction of global climate change and terrestrial ecosystem feedbacks. Using a process-based global biogeochemical model, the Dynamic Land Ecosystem Model (DLEM, we quantified simultaneously CH4 and N2O fluxes in North America's terrestrial ecosystems from 1979 to 2008. During the past 30 years, approximately 14.69 ± 1.64 T g C a−1 (1 T g = 1012 g of CH4, and 1.94 ± 0.1 T g N a−1 of N2O were released from terrestrial ecosystems in North America. At the country level, both the US and Canada acted as CH4 sources to the atmosphere, but Mexico mainly oxidized and consumed CH4 from the atmosphere. Wetlands in North America contributed predominantly to the regional CH4 source, while all other ecosystems acted as sinks for atmospheric CH4, of which forests accounted for 36.8%. Regarding N2O emission in North America, the US, Canada, and Mexico contributed 56.19%, 18.23%, and 25.58%, respectively, to the continental source over the past 30 years. Forests and croplands were the two ecosystems that contributed most to continental N2O emission. The inter-annual variations of CH4 and N2O fluxes in North America were mainly attributed to year-to-year climatic variability. While only annual precipitation was found to have a significant effect on annual CH4 flux, both mean annual temperature and annual precipitation were significantly correlated to annual N2O flux. The regional estimates and spatiotemporal patterns of terrestrial ecosystem CH4 and N2O fluxes in North America generated in this study provide useful information for global change research and policy making.

Vehicle emissions of greenhouse gases and related tracers from a tunnel study: : CO: CO2, N2O: CO2, CH4: CO2, O2: CO2 ratios, and the stable isotopes 13C and 18O in CO2 and CO

NARCIS (Netherlands)

Popa, Maria Elena; Vollmer, M. K.; Jordan, A.; Brand, W. A.; Pathirana, S. L.; Rothe, M.; Röckmann, T.

2014-01-01

Measurements of CO2, CO, N2O and CH4 mole fractions, O2/N2 ratios and the stable isotopes 13C and 18O in CO2 and CO have been performed in air samples from the Islisberg highway tunnel (Switzerland). The molar CO : CO2 ratios, with an average of (4.15 ± 0.34) ppb:ppm, are lower than reported in

Carbon dioxide induced bubble formation in a CH4-CO2-H2O ternary system: a molecular dynamics simulation study.

Science.gov (United States)

Sujith, K S; Ramachandran, C N

2016-02-07

The extraction of methane from its hydrates using carbon dioxide involves the decomposition of the hydrate resulting in a CH4-CO2-H2O ternary solution. Using classical molecular dynamics simulations, we investigate the evolution of dissolved gas molecules in the ternary system at different concentrations of CO2. Various compositions considered in the present study resemble the solution formed during the decomposition of methane hydrates at the initial stages of the extraction process. We find that the presence of CO2 aids the formation of CH4 bubbles by causing its early nucleation. Elucidation of the composition of the bubble revealed that in ternary solutions with high concentration of CO2, mixed gas bubbles composed of CO2 and CH4 are formed. To understand the role of CO2 in the nucleation of CH4 bubbles, the structure of the bubble formed was analyzed, which revealed that there is an accumulation of CO2 at the interface of the bubble and the surrounding water. The aggregation of CO2 at the bubble-water interface occurs predominantly when the concentration of CO2 is high. Radial distribution function for the CH4-CO2 pair indicates that there is an increasingly favorable direct contact between dissolved CH4 and CO2 molecules in the bubble-water interface. It is also observed that the presence of CO2 at the interface results in the decrease in surface tension. Thus, CO2 leads to greater stability of the bubble-water interface thereby bringing down the critical size of the bubble nuclei. The results suggest that a rise in concentration of CO2 helps in the removal of dissolved CH4 thereby preventing the accumulation of methane in the liquid phase. Thus, the presence of CO2 is predicted to assist the decomposition of methane hydrates in the initial stages of the replacement process.

Assessment of CH4 and N2O fluxes in a Danish Beech (Fagus sylvatica) forest and an adjacent N-fertilised barley (Hordeum vulgare)

DEFF Research Database (Denmark)

Ambus, P.; Jensen, J.M.; Prieme, A.

2001-01-01

Fluxes of CH4 and N2O were measured regularly in an agricultural field treated with 280 g m(-2) of sewage sludge. In a nearby beech forest N2O and CH4 fluxes were measured in a well-drained (dry) area and in a wet area adjacent to a drainage canal. We observed brief increases of both CH4 and N2O...... and independent of drainage status. Methane oxidation was observed all-year round in the forest cumulating to -225 mg C m(-2) and -84 mg C m(-2) in dry and wet areas. In a model experiment with incubated soil cores, nitrogen amendment (NH4Cl) and perturbation significantly reduced CH4 oxidation in the forest soil...... sludge, respectively. Four months after the sludge applications a significant effect on CO2 and NO emissions was still obvious in the field, the latter perhaps due to elevated nitrification. Nitrous oxide emission in the beech forest was about six times smaller (45 mg N m(-2)) than in the field...

Ethanol oxidation reactions catalyzed by water molecules: CH3CH2OH+n H2O→ CH3CHO+ H2+n H2O (n=0,1,2)

Science.gov (United States)

Takahashi, H.; Hisaoka, S.; Nitta, T.

2002-09-01

Ab initio density functional theory calculations have been performed to investigate the catalytic role of water molecules in the oxidation reaction of ethanol: CH3CH2OH+n H2O→ CH3CHO+ H2+n H2O (n=0,1,2) . The results show that the potential energy barrier for the reaction is 88.0 kcal/mol in case of n=0, while it is reduced by ˜34 kcal/mol when two water molecules are involved ( n=2) in the reaction. As a result, the rate constant increases to 3.31×10 -4 s-1, which shows a significant catalytic role of water molecules in the ethanol oxidation reactions.

Plasma kinetics of Ar/O2 magnetron discharge by two-dimensional multifluid modeling

International Nuclear Information System (INIS)

Costin, C.; Minea, T. M.; Popa, G.; Gousset, G.

2010-01-01

Multifluid two-dimensional model was developed to describe the plasma kinetics of the direct current Ar/O 2 magnetron, coupling two modules: charged particles and neutrals. The first module deals with three positive ions - Ar + , O 2 + , and O + - and two negative species - e - and O - - treated by the moments of Boltzmann's equation. The second one follows seven neutral species (Ar, O 2 , O, O 3 , and related metastables) by the multicomponent diffusion technique. The two modules are self-consistently coupled by the mass conservation and kinetic coefficients taking into account more than 100 volume reactions. The steady state is obtained when the overall convergence is achieved. Calculations for 10%O 2 in Ar/O 2 mixture at 2.67 and 4 Pa show that the oxygen excited species are mainly created by electron collisions in the negative glow of the discharge. Decreasing the pressure down to 0.67 Pa, the model reveals the nonlocal behavior of the reactive species. The density gradient of O 2 ground state is reversed with respect to all gradients of the other reactive species, since the latter ones originate from the molecular ground state of oxygen. It is also found that the wall reactions drastically modify the space gradient of neutral reactive species, at least as much as the pressure, even if the discharge operates in compound mode.

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...

Stabilization and reactivity of a terminal phosphidounit on Pt(II). Synthesis and X-ray structure of cationic diphelylphosphine [Pt{C6H3(CH2NMe2)2-2,6}(PHPh2)][CF3SO3] and Diphenyl-phosphido Bridged Pt(II)-Pd(II) Complex [Pt{C6H3(CH2NMe2)2-2,6} (µ-PPh2) Pd(C6H4CH2NMe2-2)(H2O)][BF4] CH2Cl2

NARCIS (Netherlands)

Koten, G. van; Maassarani, F.; Davidson, M.F.; Wehman-Ooyevaar, ICM; Grove, D.M.; Koten, M.A. van; Smeets, W.J.J.; Spek, A.L.

1995-01-01

Reaction of diphenylphosphine with the complexes [Pt(NCN)(H{2}O)]X (NCN = C{6}H{3}(CH{2}NMe{2}){2}-2, 6; X = BF{4} (1a), OSO{2}CF{3} (1b)) leads to substitution of the H{2}O ligand to afford the ionic Pt(II) complexes [Pt(NCN)(PHPh{2})]X (X = BF{4} (2a), OSO{2}CF{3} (2b)). The X-ray structure of the

Tropospheric radiative forcing of CH4

International Nuclear Information System (INIS)

Grossman, A.S.; Grant, K.E.

1994-04-01

We have evaluated the tropospheric radiative forcing of CH 4 in the 0-3000 cm -1 wavenumber range and compared this with prior published calculations. The atmospheric test cases involved perturbed methane scenarios in both a McClatchey mid latitude, summer, clear sky approximation, model atmosphere, as well as a globally and seasonally averaged model atmosphere containing a representative cloud distribution. The scenarios involved pure CH 4 radiative forcing and CH 4 plus a mixture of H 2 O, CO 2 , O 3 , and N 2 O. The IR radiative forcing was calculated using a correlated k-distribution transmission model. The major purposes of this paper are to first, use the correlated k-distribution model to calculate the tropospheric radiative forcing for CH 4 , as the only radiatively active gas, and in a mixture with H 2 O, CO 2 , O 3 , and N 2 O, for a McClatchey mid-latitude summer, clear-sky model atmosphere, and to compare the results to those obtained in the studies mentioned above. Second, we will calculate the tropospheric methane forcing in a globally and annually averaged atmosphere with and without a representative cloud distribution in order to validate the conjecture given in IPCC (1990) that the inclusion of clouds in the forcing calculations results in forcing values which are approximately 20 percent less than those obtained using clear sky approximations

Emissions of CO2, CO, NOx, HC, PM, HFC-134a, N2O and CH4 from the global light duty vehicle fleet

Directory of Open Access Journals (Sweden)

Timothy J. Wallington

2008-04-01

Full Text Available Vehicles emit carbon dioxide (CO2, carbon monoxide (CO, nitrogen oxides (NOx, hydrocarbons (HC, particulate matter (PM, hydrofluorocarbon 134a (HFC-134a, methane (CH4, and nitrous oxide (N2O. An understanding of these emissions is needed in discussions of climate change and local air pollution issues. To facilitate such discussions an overview of past, present, and likely future emissions from light duty vehicles is presented. Emission control technologies have reduced the emissions of CO, VOCs, PM, HFC-134a, CH4, and N2O from modern vehicles to very low levels.

Bimolecular reaction of CH3 + CO in solid p-H2: Infrared absorption of acetyl radical (CH3CO) and CH3-CO complex

Science.gov (United States)

Das, Prasanta; Lee, Yuan-Pern

2014-06-01

We have recorded infrared spectra of acetyl radical (CH3CO) and CH3-CO complex in solid para-hydrogen (p-H2). Upon irradiation at 248 nm of CH3C(O)Cl/p-H2 matrices, CH3CO was identified as the major product; characteristic intense IR absorption features at 2990.3 (ν9), 2989.1 (ν1), 2915.6 (ν2), 1880.5 (ν3), 1419.9 (ν10), 1323.2 (ν5), 836.6 (ν7), and 468.1 (ν8) cm-1 were observed. When CD3C(O)Cl was used, lines of CD3CO at 2246.2 (ν9), 2244.0 (ν1), 1866.1 (ν3), 1046.7 (ν5), 1029.7 (ν4), 1027.5 (ν10), 889.1 (ν6), and 723.8 (ν7) cm-1 appeared. Previous studies characterized only three vibrational modes of CH3CO and one mode of CD3CO in solid Ar. In contrast, upon photolysis of a CH3I/CO/p-H2 matrix with light at 248 nm and subsequent annealing at 5.1 K before re-cooling to 3.2 K, the CH3-CO complex was observed with characteristic IR features at 3165.7, 3164.5, 2150.1, 1397.6, 1396.4, and 613.0 cm-1. The assignments are based on photolytic behavior, observed deuterium isotopic shifts, and a comparison of observed vibrational wavenumbers and relative IR intensities with those predicted with quantum-chemical calculations. This work clearly indicates that CH3CO can be readily produced from photolysis of CH3C(O)Cl because of the diminished cage effect in solid p-H2 but not from the reaction of CH3 + CO because of the reaction barrier. Even though CH3 has nascent kinetic energy greater than 87 kJ mol-1 and internal energy ˜42 kJ mol-1 upon photodissociation of CH3I at 248 nm, its energy was rapidly quenched so that it was unable to overcome the barrier height of ˜27 kJ mol-1 for the formation of CH3CO from the CH3 + CO reaction; a barrierless channel for formation of a CH3-CO complex was observed instead. This rapid quenching poses a limitation in production of free radicals via bimolecular reactions in p-H2.

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.

Laboratory-scale measurements of N2O and CH4 emissions from hybrid poplars (Populus deltoides x Populus nigra).

Science.gov (United States)

McBain, M C; Warland, J S; McBride, R A; Wagner-Riddle, C

2004-12-01

The purpose of this study was to determine whether or not young hybrid poplar (Populus deltoides x Populus nigra) could transport landfill biogas internally from the root zone to the atmosphere, thereby acting as conduits for landfill gas release. Fluxes of methane (CH4) and nitrous oxide (N2O) from the seedlings to the atmosphere were measured under controlled conditions using dynamic flux chambers and a tunable diode laser trace gas analyser (TDLTGA). Nitrous oxide was emitted from the seedlings, but only when extremely high soil N2O concentrations were applied to the root zone. In contrast, no detectable emissions of CH4 were measured in a similar experimental trial. Visible plant morphological responses, characteristic of flood-tolerant trees attempting to cope with the negative effects of soil hypoxia, were observed during the CH4 experiments. Leaf chlorosis, leaf abscission and adventitious roots were all visible plant responses. In addition, seedling survival was observed to be highest in the biogas 'hot spot' areas of a local municipal solid waste landfill involved in this study. Based on the available literature, these observations suggest that CH4 can be transported internally by Populus deltoides x Populus nigra seedlings in trace amounts, although future research is required to fully test this hypothesis.

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.

Synthesis of flat sticky hydrophobic carbon diamond-like films using atmospheric pressure Ar/CH{sub 4} dielectric barrier discharge

Energy Technology Data Exchange (ETDEWEB)

Rincón, R., E-mail: rocio.rincon@emt.inrs.ca, E-mail: chaker@emt.inrs.ca; Matos, J. de; Chaker, M., E-mail: rocio.rincon@emt.inrs.ca, E-mail: chaker@emt.inrs.ca [Institut National de la Recherche Scientifique, 1650 Boulevard Lionel Boulet, Varennes, Québec J3X1S2 (Canada); Hendaoui, A. [Institut National de la Recherche Scientifique, 1650 Boulevard Lionel Boulet, Varennes, Québec J3X1S2 (Canada); Department of Physics, College of Science and General Studies, Alfaisal University, Takhasusi Road, Riyadh 11533 (Saudi Arabia)

2016-06-14

An Ar/CH{sub 4} atmospheric pressure dielectric barrier discharge (AP-DBD) was used to synthesize sticky hydrophobic diamond-like carbon (DLC) films on glass surface. The film is formed with plasma treatment duration shorter than 30 s, and water contact angles larger than 90° together with contact angle hysteresis larger than 10° can be achieved. According to Fourier transform infrared spectroscopy and atomic force microscopy analysis, hydrocarbon functional groups are created on the glass substrate, producing coatings with low surface energy (∼35 mJ m{sup −2}) with no modification of the surface roughness. To infer the plasma processes leading to the formation of low energy DLC surfaces, optical emission spectroscopy was used. From the results, a direct relationship between the CH species present in the plasma and the carbon concentration in the hydrophobic layer was found, which suggests that the CH species are the precursors of DLC film growth. Additionally, the plasma gas temperature was measured to be below 350 K which highlights the suitability of using AP-DBD to treat thermo-sensitive surfaces.

Diagnostic study of low-pressure Ar-O2 remote plasma generated in HCD-L 300 system: Relative density of O atom

International Nuclear Information System (INIS)

Saloum, S.; Naddaf, M.

2007-01-01

The relative density of O atom of Ar-O 2 remote plasma excited in a low pressure 13.56 HMz hollow cathode discharge system has been investigated. The measurements were carried out at a total pressure of 0.05 mbar, radiofrequency (RF) power of 200 W and at three different axial distances in the plasma chamber below the outlet of the discharge source. Using optical emission spectroscopy (OES), the relative density of O ground state was determined from intensity ratio of O(844.6 nm) and Ar(750.4 nm) lines. The electron temperature and O 2 + densities have been measured using double langmuir probe measurements. The kinetic study of Ar-O 2 plasma, combined with both spectroscopy and langmuir probe measurements, revealed that the main production mechanism of the excited O(3p 3 P) is direct excitation by electron impact. A maximum of O ground state relative density and correspondingly a minimum of O 2 + density are obtained for the ratio O 2 /Ar: 60/40. The maximum O density in the remote zone is found to be 4.5 times higher than at the outlet of source. (author)

Infinitely high etch selectivity during CH4/H2/Ar inductively coupled plasma (ICP) etching of indium tin oxide (ITO) with photoresist mask

International Nuclear Information System (INIS)

Kim, D.Y.; Ko, J.H.; Park, M.S.; Lee, N.-E.

2008-01-01

Under certain conditions during ITO etching using CH 4 /H 2 /Ar inductively coupled plasmas, the etch rate selectivity of ITO to photoresist (PR) was infinitely high because the ITO films continued to be etched, but a net deposition of the α-C:H layer occurred on the top of the PR. Analyses of plasmas and etched ITO surfaces suggested that the continued consumption of the carbon and hydrogen in the deposited α-C:H layer by their chemical reaction with In and Sn atoms in the ITO resulting in the generation of volatile metal-organic etch products and by the ion-enhanced removal of the α-C:H layer presumably play important roles in determining the ITO etch rate and selectivity

Olefins metathesis, synthesis and properties of homogeneous models of the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst; Methathese des olefines, synthese et proprietes des modeles homogenes du catalyseur Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Doledec, G.

1999-10-05

The aim of this work was to synthesize and to study homogeneous models of the rhenium oxide on alumina catalyst in order to better understand the influence of the alumina environment over the activity in olefin metathesis. A series of aluminium complexes (ArO){sub 2}Al-Y have been synthesised, where ArO is a 4-substituted-2,6-di-tert-butyl-phenoxy, or (ArO){sub 2} is a CH{sub 2{sup -}} or S-ortho bridged-4,4'-di-tert-butyl-di-phenoxy, and Y is an alkyl or chlorine ligand. The reaction of (ArO){sub 2}Al-Cl with AgReO{sub 4} led to new complexes (ArO){sub 2}Al-OReO{sub 3} (A). These complexes exhibit a low to moderate activity in metathesis of 2-pentene (TOF = 0,5 min{sup -1} at 25 deg. C in a toluene solution). Complexes (ArO){sub 2}Al-R (R = iBu, Et) react with Re{sub 2}O{sub 7} in THF or dioxane giving type B complexes including oligomeric linkages like O{sub 3}Re-[Al(OAr)-O){sub 2}-ReO{sub 3}. They show a fairly high activity in the metathesis of 2-pentene, with TOF values as high as 100 min{sup -1}. As far as we know, these are the most active rhenium-based homogeneous metathesis catalysts. Complexes type A may be converted into type B complexes upon reaction with (ArO){sub 2}Al-R in an ether solvent. The high activity of B complexes is tentatively related to the Al-O-Al linkages that are molecular in the homogeneous models or present at the surface of the alumina in the heterogeneous catalyst. These results bear out again the role of the Lewis acidity in these catalysts. We used (ArO){sub 2}Al-R complexes to modify the heterogenous catalyst. It appears that it is an excellent way to reduce the rhenium loading without any loss of activity. (author)

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

Science.gov (United States)

Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

2009-11-04

(PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

SYNTHESIS AND CHARACTERIZATION OF (MU-5-C5ME5)2TI(R)CL (R = ME, ET, NORMAL-PR, CH=CH2, PH, O-NORMAL-PR) AND THEIR SALT METATHESIS REACTIONS - THERMAL-DECOMPOSITION PATHWAYS OF (MU-5-C5ME5)2TI(ME)R' (R' = ET, CH=CH2, PH, CH2PH)

NARCIS (Netherlands)

LUINSTRA, GA; TEUBEN, JH

Complexes Cp*2Ti(R)Cl (Cp* = eta-5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (4), Ph (5), O-n-Pr (6)) have been prepared by oxidation Of CP*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R. was observed. Homolysis of

New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

Science.gov (United States)

Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

2013-02-18

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

Effect of subcritical CO{sub 2} on ionic conductivity of (Al[O(CH{sub 2}CH{sub 2}O){sub 8.7}]{sub r}/(LiClO{sub 4}){sub z}){sub n} hybrid inorganic-organic networks

Energy Technology Data Exchange (ETDEWEB)

Vezzu, Keti; Bertucco, Alberto [Universita di Padova, Padova (Italy). Dipartimento di Principi e Impianti di Ingegneria Chimica ' I. Sorgato' ; Zago, Vanni; Vittadello, Michele; Noto, Vito Di [Universita di Padova, Padova (Italy). Dipartimento di Scienze Chimiche

2006-01-20

The aim of this work is to study the effect of CO{sub 2} under pressure on hybrid inorganic-organic polymer electrolytes, by using broad band dielectric spectroscopy (BDS) in the frequency interval 40Hz-10MHz and in the temperature range of -80 to 120{sup o}C. Eleven inorganic-organic hybrid materials of the ORMOCERs type, with general formula (Al[O(CH{sub 2}CH{sub 2}O){sub 8.7}]{sub r}/(LiClO{sub 4}){sub z}){sub n} were treated by applying CO{sub 2} at 293K and 5MPa. The results demonstrated that the CO{sub 2} treatment generally depressed the conductivity of about one order of magnitude. The decreased conductivity in treated complexes is explained in terms of a smaller anion-trapping ability of the Al centers. Residual CO{sub 2} molecules are likely to inhibit the interaction of the perchlorate anions with Al centers within the structure. Segmental motion of the polymer chains plays a crucial role in the conductivity of investigated samples, while the ion-hopping phenomenon is the most important charge transfer mechanism both in the pristine and CO{sub 2} treated materials. Equivalent conductivity studies have elucidated the different ionic species present at various salt concentrations and gave insight about the role of CO{sub 2} in modifying the transport properties of the samples. (author)

Anthropogenic effects on greenhouse gas (CH{sub 4} and N{sub 2}O) emissions in the Guadalete River Estuary (SW Spain)

Energy Technology Data Exchange (ETDEWEB)

Burgos, M.; Sierra, A.; Ortega, T.; Forja, J.M.

2015-01-15

Coastal areas are subject to a great anthropogenic pressure because more than half of the world's population lives in its vicinity causing organic matter inputs, which intensifies greenhouse gas emissions into the atmosphere. Dissolved concentrations of CH{sub 4} and N{sub 2}O have been measured seasonally during 2013 in the Guadalete River Estuary, which flows into the Cadiz Bay (southwestern Spanish coast). It has been intensely contaminated since 1970. Currently it receives wastewater effluents from cities and direct discharges from nearby agriculture crop. Eight sampling stations have been established along 18 km of the estuary. CH{sub 4} and N{sub 2}O were measured using a gas chromatograph connected to an equilibration system. Additional parameters such as organic matter, dissolved oxygen, nutrients and chlorophyll were determinate as well, in order to understand the relationship between physicochemical and biological processes. Gas concentrations increased from the River mouth toward the inner part, closer to the wastewater treatment plant discharge. Values varied widely within 21.8 and 3483.4 nM for CH{sub 4} and between 9.7 and 147.6 nM for N{sub 2}O. Greenhouse gas seasonal variations were large influenced by the precipitation regime, masking the temperature influence. The Guadatete Estuary acted as a greenhouse gas source along the year, with mean fluxes of 495.7 μmol m{sup −2} d{sup −1} and 92.8 μmol m{sup −2} d{sup −1} for CH{sub 4} and N{sub 2}O, respectively. - Highlights: • The estuary acts as a source of atmospheric methane and nitrous oxide. • Anthropogenic inputs affect the distribution of the greenhouse gases. • Dissolved gases presented an important longitudinal gradient. • Seasonal variations highly depended on the precipitation regimen.

Effects of phosphorus addition on nitrogen cycle and fluxes of N2O and CH4 in tropical tree plantation soils in Thailand

Directory of Open Access Journals (Sweden)

Taiki Mori

2017-04-01

Full Text Available An incubation experiment was conducted to test the effects of phosphorus (P addition on nitrous oxide (N2O emissions and methane (CH4 uptakes, using tropical tree plantation soils in Thailand. Soil samples were taken from five forest stands—Acacia auriculiformis, Acacia mangium, Eucalyptus camaldulensis, Hopea odorata, and Xylia xylocarpa—and incubated at 80% water holding capacity. P addition stimulated N2O emissions only in Xylia xylocarpa soils. Since P addition tended to increase net ammonification rates in Xylia xylocarpa soils, the stimulated N2O emissions were suggested to be due to the stimulated nitrogen (N cycle by P addition and the higher N supply for nitrification and denitrification. In other soils, P addition had no effects on N2O emissions or soil N properties, except that P addition tended to increase the soil microbial biomass N in Acacia auriculiformis soils. No effects of P addition were observed on CH4 uptakes in any soil. It is suggested that P addition on N2O and CH4 fluxes at the study site were not significant, at least under laboratory conditions.

Atmospheric chemistry of CF3CH2CH2OH

DEFF Research Database (Denmark)

Hurley, Michael D.; Misner, Jessica A.; Ball, James C.

2005-01-01

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF3CH2C(O)H and CF3CH2CH2OH in 700 Torr of N-2 or air diluent at 296 2 K. The rate constants determined were k(Cl+CF3CH2C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF3CH2C(O)H) = (2.57 +/- 0.44...

Combined CO/CH4 oxidation tests over Pd/Co3O4 monolithic catalyst. Effects of high reaction temperature and SO2 exposure on the deactivation process

International Nuclear Information System (INIS)

Liotta, L.F.; Venezia, A.M.; Di Carlo, G.; Pantaleo, G.; Deganello, G.; Merlone Borla, E.; Pidria, M.

2007-01-01

CO and CH 4 combined oxidation tests were performed over a Pd (70 g/ft 3 )/Co 3 O 4 monolithic catalyst in conditions of GHSV = 100,000 h -1 and feed composition close to that of emission from bi-fuel vehicles. The effect of SO 2 (5 ppm) on CO and CH 4 oxidation activity under lean condition (λ 2) was investigated. The presence of sulphur strongly deactivated the catalyst towards methane oxidation, while the poisoning effect was less drastic in the oxidation of CO. Saturation of the Pd/Co 3 O 4 catalytic sites via chemisorbed SO 3 and/or sulphates occurred upon exposure to SO 2 . A treatment of regeneration to remove sulphate species was attempted by performing a heating/cooling cycle up to 900 C in oxidizing atmosphere. Decomposition of PdO and Co 3 O 4 phases at high temperature, above 750 C, was observed. Moreover, sintering of Pd 0 and PdO particles along with of CoO crystallites takes place. (author)

Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

Science.gov (United States)

Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

2016-11-17

The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

Characteristics of SiO{sub 2} etching with a C{sub 4}F{sub 8}/Ar/CHF{sub 3}/O{sub 2} gas mixture in 60-MHz/2-MHz dual-frequency capacitively coupled plasmas

Energy Technology Data Exchange (ETDEWEB)

Jeon, M. H.; Kang, S. K.; Park, J. Y.; Yeom, G. Y. [Sungkyunkwan University, Suwon (Korea, Republic of)

2011-11-15

Nanoscale SiO{sub 2} contact holes were etched by using C{sub 4}F{sub 8}/CHF{sub 3}/O{sub 2}/Ar gas mixtures in dual frequency capacitively coupled plasmas (DF-CCPs) where a 60-MHz source power was applied to the top electrode while a 2-MHz bias power was applied to the bottom electrode. The initial increase in the CHF{sub 3} gas flow rate at a fixed CHF{sub 3}+O{sub 2} flow rate increased the SiO{sub 2} etch rate as well as SiO{sub 2} etch selectivity over that of the amorphous carbon layer (ACL). When the high-frequency (HF) power was increased both SiO{sub 2} etch rate and the etch selectivity over ACL were increased. For a 300 W/500 W power ratio of 60-MHz HF power/ 2-MHz low-freqeuncy (LF) and a gas mixture of Ar (140 sccm) /C{sub 4}F{sub 8} (30 sccm) /CHF{sub 3} (25 sccm) /O{sub 2} (5 sccm) while maintaining 20 mTorr, an anisotropic etch profile with an SiO{sub 2} etch rate of 3350 A/min and an etch selectivity of higher than 6 over ACL could be obtained.

Plasma kinetics of Ar/O{sub 2} magnetron discharge by two-dimensional multifluid modeling

Energy Technology Data Exchange (ETDEWEB)

Costin, C.; Minea, T. M.; Popa, G.; Gousset, G. [LPGP, UMR 8578, CNRS-Paris-Sud XI University, Bat. 210, Orsay Cedex 91405, France and Faculty of Physics, Al. I. Cuza University, 11 Carol I Blvd., Iasi 700506 (Romania); LPGP, UMR 8578, CNRS-Paris-Sud XI University, Bat. 210, Orsay Cedex 91405 (France); Faculty of Physics, Al. I. Cuza University, 11 Carol I Blvd., Iasi 700506 (Romania); LPGP, UMR 8578, CNRS-Paris-Sud XI University, Bat. 210, Orsay Cedex 91405 (France)

2010-03-15

Multifluid two-dimensional model was developed to describe the plasma kinetics of the direct current Ar/O{sub 2} magnetron, coupling two modules: charged particles and neutrals. The first module deals with three positive ions - Ar{sup +}, O{sub 2}{sup +}, and O{sup +} - and two negative species - e{sup -} and O{sup -} - treated by the moments of Boltzmann's equation. The second one follows seven neutral species (Ar, O{sub 2}, O, O{sub 3}, and related metastables) by the multicomponent diffusion technique. The two modules are self-consistently coupled by the mass conservation and kinetic coefficients taking into account more than 100 volume reactions. The steady state is obtained when the overall convergence is achieved. Calculations for 10%O{sub 2} in Ar/O{sub 2} mixture at 2.67 and 4 Pa show that the oxygen excited species are mainly created by electron collisions in the negative glow of the discharge. Decreasing the pressure down to 0.67 Pa, the model reveals the nonlocal behavior of the reactive species. The density gradient of O{sub 2} ground state is reversed with respect to all gradients of the other reactive species, since the latter ones originate from the molecular ground state of oxygen. It is also found that the wall reactions drastically modify the space gradient of neutral reactive species, at least as much as the pressure, even if the discharge operates in compound mode.

Measurements of N2O and CH4 from the aerated composting of food waste

International Nuclear Information System (INIS)

He, Y.; Sun, T.; Inamori, Y.; Mizuochi, M.; Kong, H.; Iwami, N.

2000-01-01

Emissions of N 2 O and CH 4 from an aerated composting system were investigated using small-scale simulated reactors. The results show relatively high emissions of N 2 O at the beginning of composting, in proportion to the application amount of food waste. After 2 days, the N 2 O emission decreased to 0.53 ppmv on average, near to the background level in the atmosphere (0.45 ppmv). The addition of composted cattle manure increased N 2 O emissions not only at the beginning of composting, but also during the later period and resulted in two peak emission curves. Good correlation was observed between the N 2 O concentration at the air outlet and NO 2 - concentration in waste, suggesting a generation pathway for N 2 O from NO 2 - to N 2 O. Methane was only detected in treatments containing composted cattle manure. The high emission of methane illustrates the involvement of anoxic/anaerobic microorganisms with the addition of composted manure. The result suggests the existence of anoxic or anaerobic microsite inside the waste particles even though ventilation was employed during the composting process

Impacts of climate and land use on N2 O and CH4 fluxes from tropical ecosystems in the Mt. Kilimanjaro region, Tanzania.

Science.gov (United States)

Gütlein, Adrian; Gerschlauer, Friederike; Kikoti, Imani; Kiese, Ralf

2018-03-01

In this study, we quantify the impacts of climate and land use on soil N 2 O and CH 4 fluxes from tropical forest, agroforest, arable and savanna ecosystems in Africa. To do so, we measured greenhouse gases (GHG) fluxes from 12 different ecosystems along climate and land-use gradients at Mt. Kilimanjaro, combining long-term in situ chamber and laboratory soil core incubation techniques. Both methods showed similar patterns of GHG exchange. Although there were distinct differences from ecosystem to ecosystem, soils generally functioned as net sources and sinks for N 2 O and CH 4 respectively. N 2 O emissions correlated positively with soil moisture and total soil nitrogen content. CH 4 uptake rates correlated negatively with soil moisture and clay content and positively with SOC. Due to moderate soil moisture contents and the dominance of nitrification in soil N turnover, N 2 O emissions of tropical montane forests were generally low (<1.2 kg N ha -1  year -1 ), and it is likely that ecosystem N losses are driven instead by nitrate leaching (~10 kg N ha -1  year -1 ). Forest soils with well-aerated litter layers were a significant sink for atmospheric CH 4 (up to 4 kg C ha -1  year -1 ) regardless of low mean annual temperatures at higher elevations. Land-use intensification significantly increased the soil N 2 O source strength and significantly decreased the soil CH 4 sink. Compared to decreases in aboveground and belowground carbon stocks enhanced soil non-CO 2 GHG emissions following land-use conversion from tropical forests to homegardens and coffee plantations were only a small factor in the total GHG budget. However, due to lower ecosystem carbon stock changes, enhanced N 2 O emissions significantly contributed to total GHG emissions following conversion of savanna into grassland and particularly maize. Overall, we found that the protection and sustainable management of aboveground and belowground carbon and nitrogen stocks of agroforestry and

High temporal resolution ecosystem CH4, CO2 and H2O flux data measured with a novel chamber technique

Science.gov (United States)

Steenberg Larsen, Klaus; Riis Christiansen, Jesper

2016-04-01

Soil-atmosphere exchange of greenhouse gases (GHGs) is commonly measured with closed static chambers (Pihlatie et al., 2013) with off-site gas chromatographic (GC) analysis for CH4 and N2O. Static chambers are widely used to observe in detail the effect of experimental manipulations, like climate change experiments, on GHG exchange (e.g. Carter et al., 2012). However, the low sensitivity of GC systems necessitates long measurement times and manual sampling, which increases the disturbance of the exchange of GHGs and leads to potential underestimation of fluxes (Christiansen et al., 2011; Creelman et al., 2013). The recent emergence of field proof infrared lasers using cavity ring-down spectroscopy (CRDS) have increased frequency and precision of concentration measurements and enabled better estimates of GHG fluxes (Christiansen et al., 2015) due to shorter chamber enclosure times. This minimizes the negative impact of the chamber enclosure on the soil-atmosphere gas exchange rate. Secondly, an integral aspect of understanding GHG exchange in terrestrial ecosystem is to achieve high temporal coverage. This is needed to capture the often dynamic behavior where fluxes can change rapidly over the course of days or even a few hours in response to e.g. rain events. Consequently, low temporal coverage in measurements of GHG exchange have in many past investigations led to highly uncertain annual budgets which severely limits our understanding of the ecosystem processes interacting with the climate system through GHG exchange. Real-time field measurements at high temporal resolution are needed to obtain a much more detailed understanding of the processes governing ecosystem CH4 exchange as well as for better predicting the effects of climate and environmental changes. We combined a state-of-the-art field applicable CH4 sensor (Los Gatos UGGA) with a newly developed ecosystem-level automatic chamber controlled by a LI-COR 8100/8150 system. The chamber is capable of

Proton scattering from unstable nuclei 20O, 30S, 34Ar: experimental study and models

International Nuclear Information System (INIS)

Khan, Elias

2000-01-01

Elastic and inelastic proton scattering from the unstable nuclei 20 O, 30 S and 34 Ar were measured in inverse kinematics at the Grand Accelerateur National d'Ions Lourds. Secondary beams of 20 O at 43 MeV/A, 30 S at 53 MeV/A and 34 Ar at 47 MeV/A impinged on a (CH 2 ) n target. Recoiling protons were detected in the silicon strip array MUST. Energies and angular distributions of the first 2 + and 3 - states were measured. A phenomenological analysis yields values of the deformation parameters β 2 and β 3 of 0.55 (6) and 0.35 (5) for 20 O, 0.32 (3) and 0.22 (4) for 30 S, 0.27 (2) and 0.39 (3) for 34 Ar, respectively, and allows the extraction of the ratio of neutron to proton transition matrix elements (M n /M p )/(N/Z) for 2 + states: 2.35 (37) for 20 O, 0.93 (20) for 30 S and 1.35 (28) for 34 Ar. Therefore the proton rich nuclei 30 S and 34 Ar show a 2 + excitation of isoscalar character whereas the excitation of 20 O is of isovector character. In order to perform a microscopic analysis of the data, we have developed a QRPA model, using three Skyrme interaction: SIII, SG2, SLy4. This model reproduces measured B(EL) values for the oxygen, sulfur and argon isotopic chains, whereas RPA calculations, which do not take pairing into account, underestimate these values. In the case of the QRPA model the energies of the first 2 + state are overestimated by about 1 MeV, but the evolution along the isotopic chains is well reproduced. (M n /M p )/(N/Z) ratios for the first 2 + state deduced from the microscopic analysis using QRPA are 1.98 for 20 O, 1.05 for 30 S and 1.00 for 34 Ar, in agreement with the conclusions of the phenomenological analysis. However important discrepancies are observed between the two types of analysis for other isotopes, in particular neutron rich argon and sulfur nuclei. (author)

On the use of satellite-derived CH4 : CO2 columns in a joint inversion of CH4 and CO2 fluxes

NARCIS (Netherlands)

Pandey, S.

2015-01-01

We present a method for assimilating total column CH4 : CO2 ratio measurements from satellites for inverse modeling of CH4 and CO2 fluxes using the variational approach. Unlike conventional approaches, in which retrieved CH4 : CO2 are multiplied by model-derived total column CO2 and only the

The new Mediterranean background monitoring station of Ersa, Cape Corsica: A long term Observatory component of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx)

Science.gov (United States)

Dulac, Francois

2013-04-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr/) is a French initiative supported by the MISTRALS program (Mediterranean Integrated Studies at Regional And Locals Scales, http://www.mistrals-home.org). It aims at a scientific assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The major stake is an understanding of the future of the Mediterranean region in a context of strong regional anthropogenic and climatic pressures. The target of ChArMEx is short-lived particulate and gaseous tropospheric trace species which are the cause of poor air quality events, have two-way interactions with climate, or impact the marine biogeochemistry. In order to fulfill these objectives, important efforts have been put in 2012 in order to implement the infrastructure and instrumentation for a fully equipped background monitoring station at Ersa, Cape Corsica, a key location at the crossroads of dusty southerly air masses and polluted outflows from the European continent. The observations at this station began in June 2012 (in the context of the EMEP / ACTRIS / PEGASOS / ChArMEx campaigns). A broad spectrum of aerosol properties is also measured at the station, from the chemical composition (off-line daily filter sampling in PM2.5/PM10, on-line Aerosol Chemical Speciation Monitor), ground optical properties (extinction/absorption/light scattering coeff. with 1-? CAPS PMex monitor, 7-? Aethalometer, 3-? Nephelometer), integrated and vertically resolved optical properties (4-? Cimel sunphotometer and LIDAR, respective), size distribution properties (N-AIS, SMPS, APS, and OPS instruments), mass (PM1/PM10 by TEOM/TEOM-FDMS), hygroscopicity (CCN), as well as total insoluble deposition. So far, real-time measurement of reactive gases (O3, CO, NO, NO2), and off-line VOC measurements (cylinders, cartridges) are also

Linking rhizospheric CH₄ oxidation and net CH₄ emissions in an arctic wetland based on ¹³CH₄ labeling of mesocosms

DEFF Research Database (Denmark)

Nielsen, Cecilie Skov; Michelsen, Anders; Ambus, Per

2017-01-01

Aims: Poorly drained arctic ecosystems are potential large emitters of methane (CH4) due to their high soil organic carbon content and low oxygen availability. In wetlands, aerenchymatous plants transport CH4 from the soil to the atmosphere, but concurrently transport O2 to the rhizosphere, which...... may lead to oxidation of CH4. The importance of the latter process is largely unknown for arctic plant species and ecosystems. Here, we aim to quantify the subsurface oxidation of CH4 in a waterlogged arctic ecosystem dominated by Carex aquatilis ssp. stans and Eriophorum angustifolium, and evaluate...... during three weeks after addition of 13C-enriched CH4 below the mesocosm. Results: Most of the recovered 13C label (>98 %) escaped the ecosystem as CH4, while less than 2 % was oxidized to 13CO2. Conclusions: It is concluded that aerenchymatous plants control the overall CH4 emissions but, as a transport...

The role of carboxylato ligand dissociation in the oxidation of chrysin with H2O2 catalysed by [Mn-2 (III, IV)(mu-CH3COO)(mu-O)(2)(Me(4)dtne)](PF6)(2)

NARCIS (Netherlands)

Abdolahzadeh, Shaghayegh; Boyle, Nicola M.; Hoogendijk, M. Lisa; Hage, Ronald; de Boer, Johannes W.; Browne, Wesley R.

2014-01-01

The aqueous and non-aqueous chemistry of the complex [Mn-2 (III,IV)(mu-CH3COO)(mu-O)(2)(Me(4)dtne)](PF6)(2) (where Me(4)dtne = 1,2-bis(4,7-dimethyl- 1,4,7-triazacyclonon-1-yl) ethane), which has been demonstrated as an exceptionally active catalyst in the bleaching of raw cotton and especially wood

Theoretical study of EPR spectra in Cu2+ - and Mn2+ - doped CaCd(CH3COO)4.6H2O

International Nuclear Information System (INIS)

Zhou Yiyang; Zhao Minguang

1987-08-01

The EPR spectra of CaCd(CH 3 COO) 4 .6H 2 O doped with Cu 2+ and Mn 2+ have been studied theoretically. A comparison between the calculated results and the experimental data shows quantitatively that the Cu 2+ and Mn 2+ ions substitute for the Cd 2+ and Ca 2+ ions, respectively. This conclusion is consistent with the qualitative assumption given by previous authors. (author). 36 refs, 1 fig., 3 tabs

Sequential Ar-O2 sputtering of Y2O3, BaF2, and CuO targets for preparation of Y-Ba-Cu-O superconducting films without wet-O2 annealing

International Nuclear Information System (INIS)

Bhushan, M.; Strauss, A.J.; Finn, M.C.

1989-01-01

Superconducting Y-Ba-Cu-O (YBCO) films have been prepared by ex situ O 2 annealing of multilayer films deposited on yttria-stabilized zirconia substrates by sequential rf diode sputtering of Y 2 O 3 , BaF 2 , and CuO targets, all of which are chemically stable. If sputtering is performed in an Ar ambient, the as-deposited films contain sufficient F to require its removal by annealing in wet O 2 at about 800 degree C or above before the superconducting YBCO phase can be formed by annealing in dry O 2 . However, sputtering in an Ar-O 2 ambient greatly reduces the F content, making it possible to obtain the superconducting phase by annealing in dry O 2 only. If the ambient contains about 20% O 2 , films with T c (R=0)>85 K can be prepared without wet-O 2 annealing. The Ar-O 2 process therefore has the potential for in situ preparation of superconducting YBCO films

High catalytic activity and stability of Ni/CexZr1-xO2/MSU-H for CH4/CO2 reforming reaction

Science.gov (United States)

Chang, Xiaoqian; Liu, Bingsi; Xia, Hong; Amin, Roohul

2018-06-01

How to reduce emission of CO2 as greenhouse gases, which resulted in global warming, is of very important significance. A series of Ni/CexZr1-xO2/MSU-H catalysts was prepared by means of hexagonally ordered mesoporous MSU-H with thermal and hydrothermal stabilities, which is cheap and can be synthesized in the large scale. The 10%Ni/Ce0.75Zr0.25O2/MSU-H catalyst presents high catalytic activity, stability and the ability of coke-resistance for CH4/CO2 reforming reaction due to high SBET (428 m2/g) and smaller Nio nanoparticle size (3.14 nm). The high dispersed Nio nanoparticles over MSU-H promoted the decomposition of CH4 and the carbon species accumulated on active Nio sites reacting with crystal lattice oxygen in Ce0.75Zr0.25O2 to form CO molecules. In the meantime, the remained oxygen vacancies on the interface between Nio and Ce0.75Zr0.25O2 could be supplemented via CO2. HRTEM images and XRD results of Ni/Ce0.75Zr0.25O2/MSU-H verified that high dispersion of Ni nanoparticles over Ni/Ce0.75Zr0.25O2/MSU-H correlated closely with the synergistic action between Ce0.75Zr0.25O2 and MSU-H as well as hexagonally ordered structure of MSU-H, which can provide effectively the oxygen storage capacity and inhibit the formation of coke.

Atmospheric chemistry of CH3CHF2 (R-152a): mechanism of the CH3CF2O2+HO2 reaction

DEFF Research Database (Denmark)

Hashikawa, Y; Kawasaki, M; Andersen, Mads Peter Sulbæk

2004-01-01

FTIR smog chamber techniques have been used to investigate the mechanism of the reaction of CH3CF2O2 with HO2 radicals in 100-700 Torr of synthetic air at 296 K. The reaction gives CH3CF2OOH and COF2 in molar yields of 0.53 +/- 0.05 and 0.47 +/- 0.05, respectively. Results are discussed with resp......FTIR smog chamber techniques have been used to investigate the mechanism of the reaction of CH3CF2O2 with HO2 radicals in 100-700 Torr of synthetic air at 296 K. The reaction gives CH3CF2OOH and COF2 in molar yields of 0.53 +/- 0.05 and 0.47 +/- 0.05, respectively. Results are discussed...

Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ

2004-01-01

Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k......(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further...... oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials...

Uncertainty in CH4 and N2O emission estimates from a managed fen meadow using EC measurements

International Nuclear Information System (INIS)

Kroon, P.S.; Hensen, A.; Van 't Veen, W.H.; Vermeulen, A.T.; Jonker, H.

2009-02-01

The overall uncertainty in annual flux estimates derived from chamber measurements may be as high as 50% due to the temporal and spatial variability in the fluxes. As even a large number of chamber plots still cover typically less than 1% of the total field area, the field-scale integrated emission necessarily remains a matter of speculation. High frequency micrometeorological methods are a good option for obtaining integrated estimates on a hectare scale with a continuous coverage in time. Instrumentation is now becoming available that meets the requirements for CH4 and N2O eddy covariance (EC) measurements. A system consisting of a quantum cascade laser (QCL) spectrometer and a sonic anemometer has recently been proven to be suitable for performing EC measurements. This study analyses the EC flux measurements of CH4 and N2O and its corrections, like calibration, Webb-correction, and corrections for high and low frequency losses, and assesses the magnitude of the uncertainties associated with the precision of the measurement instruments, measurement set-up and the methodology. The uncertainty of one single EC flux measurement, a daily, monthly and 3-monthly average EC flux is estimated. In addition, the cumulative emission of C-CH4 and N-N2O and their uncertainties are determined over several fertilizing events at a dairy farm site in the Netherlands. These fertilizing events are selected from the continuously EC flux measurements from August 2006 to September 2008. The EC flux uncertainties are compared by the overall uncertainty in annual flux estimates derived from chamber measurements. It will be shown that EC flux measurements can decrease the overall uncertainty in annual flux estimates

Uncertainty in CH4 and N2O emission estimates from a managed fen meadow using EC measurements

Energy Technology Data Exchange (ETDEWEB)

Kroon, P.S.; Hensen, A.; Van ' t Veen, W.H.; Vermeulen, A.T. [ECN Biomass, Coal and Environment, Petten (Netherlands); Jonker, H. [Delft University of Technology, Delft (Netherlands)

2009-02-15

The overall uncertainty in annual flux estimates derived from chamber measurements may be as high as 50% due to the temporal and spatial variability in the fluxes. As even a large number of chamber plots still cover typically less than 1% of the total field area, the field-scale integrated emission necessarily remains a matter of speculation. High frequency micrometeorological methods are a good option for obtaining integrated estimates on a hectare scale with a continuous coverage in time. Instrumentation is now becoming available that meets the requirements for CH4 and N2O eddy covariance (EC) measurements. A system consisting of a quantum cascade laser (QCL) spectrometer and a sonic anemometer has recently been proven to be suitable for performing EC measurements. This study analyses the EC flux measurements of CH4 and N2O and its corrections, like calibration, Webb-correction, and corrections for high and low frequency losses, and assesses the magnitude of the uncertainties associated with the precision of the measurement instruments, measurement set-up and the methodology. The uncertainty of one single EC flux measurement, a daily, monthly and 3-monthly average EC flux is estimated. In addition, the cumulative emission of C-CH4 and N-N2O and their uncertainties are determined over several fertilizing events at a dairy farm site in the Netherlands. These fertilizing events are selected from the continuously EC flux measurements from August 2006 to September 2008. The EC flux uncertainties are compared by the overall uncertainty in annual flux estimates derived from chamber measurements. It will be shown that EC flux measurements can decrease the overall uncertainty in annual flux estimates.

A brief overview of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx) database and campaign operation centre (ChOC)

Science.gov (United States)

Ferré, Hélène; Dulac, François; Belmahfoud, Nizar; Brissebrat, Guillaume; Cloché, Sophie; Descloitres, Jacques; Fleury, Laurence; Focsa, Loredana; Henriot, Nicolas; Ramage, Karim; Vermeulen, Anne

2016-04-01

Initiated in 2010 in the framework of the multidisciplinary research programme MISTRALS (Mediterranean Integrated Studies at Regional and Local Scales; http:www.mistrals-home.org), the Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr/) aims at federating the scientific community for an updated assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The project combines mid- and long-term monitoring, intensive field campaigns, use of satellite data, and modelling studies. In this presentation we provide an overview of the campaign operation centre (http://choc.sedoo.fr/) and project database (http://mistrals.sedoo.fr/ChArMEx), at the end of the first experimental phase of the project that included a series of large campaigns based on airborne means (including balloons and various aircraft) and a network of surface stations. Those campaigns were performed mainly in the western Mediterranean basin in the summer of 2012, 2013 and 2014 with the help of the ChArMEx Operation Centre (ChOC), an open web site that has the objective to gather and display daily quick-looks from model forecasts and near-real time in situ and remote sensing observations of physical and chemical weather conditions relevant for the everyday campaign operation decisions. The ChOC is also useful for post campaign analyses and can be completed with a number of quick-looks of campaign results obtained later in order to offer an easy access to, and comprehensive view of all available data during the campaign period. The items included are selected according to the objectives and location of the given campaigns. The second experimental phase of ChArMEx from 2015 on is more focused on the eastern basin. In addition, the project operation centre is planned to be adapted for a joint MERMEX-ChArMEx oceanographic cruise (PEACETIME) for a study at

Fluorocarbon assisted atomic layer etching of SiO{sub 2} and Si using cyclic Ar/C{sub 4}F{sub 8} and Ar/CHF{sub 3} plasma

Energy Technology Data Exchange (ETDEWEB)

Metzler, Dominik; Oehrlein, Gottlieb S., E-mail: oehrlein@umd.edu [Department of Materials Science and Engineering, and Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20740 (United States); Li, Chen [Department of Physics, and Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20740 (United States); Engelmann, Sebastian; Bruce, Robert L.; Joseph, Eric A. [IBM T. J. Watson Research Center, Yorktown Heights, New York 10598 (United States)

2016-01-15

The need for atomic layer etching (ALE) is steadily increasing as smaller critical dimensions and pitches are required in device patterning. A flux-control based cyclic Ar/C{sub 4}F{sub 8} ALE based on steady-state Ar plasma in conjunction with periodic, precise C{sub 4}F{sub 8} injection and synchronized plasma-based low energy Ar{sup +} ion bombardment has been established for SiO{sub 2} [Metzler et al., J. Vac. Sci. Technol. A 32, 020603 (2014)]. In this work, the cyclic process is further characterized and extended to ALE of silicon under similar process conditions. The use of CHF{sub 3} as a precursor is examined and compared to C{sub 4}F{sub 8}. CHF{sub 3} is shown to enable selective SiO{sub 2}/Si etching using a fluorocarbon (FC) film build up. Other critical process parameters investigated are the FC film thickness deposited per cycle, the ion energy, and the etch step length. Etching behavior and mechanisms are studied using in situ real time ellipsometry and x-ray photoelectron spectroscopy. Silicon ALE shows less self-limitation than silicon oxide due to higher physical sputtering rates for the maximum ion energies used in this work, ranged from 20 to 30 eV. The surface chemistry is found to contain fluorinated silicon oxide during the etching of silicon. Plasma parameters during ALE are studied using a Langmuir probe and establish the impact of precursor addition on plasma properties.

Spatial variability of greenhouse gases emissions (CO2, CH4, N2O) in a tropical hydroelectric reservoir flooding primary forest (Petit Saut Reservoir, French Guiana)

Science.gov (United States)

Cailleaud, Emilie; Guérin, Frédéric; Bouillon, Steven; Sarrazin, Max; Serça, Dominique

2014-05-01

At the Petit Saut Reservoir (PSR, French Guiana, South America), vertical profiles were performed at 5 stations in the open waters (OW) and 6 stations in two shallow flooded forest (FF) areas between April 2012 and September 2013. Measurements included physico-chemical parameters, ammonium, nitrate and dissolved greenhouse gas (CO2, CH4, N2O) concentrations, dissolved and particulate organic carbon (DOC, POC) and nitrogen (PN), δ13C-POC and δ15N-PN . The diffusive fluxes were calculated from surface concentrations. The aim of this study was to estimate the spatial variations of greenhouse gas emissions at a dentrical hydroelectric reservoir located in the tropics and flooding primary forest. Twenty years after impoundment, the water column of the PSR is permanently and tightly stratified thermally in the FF whereas in the OW, the thermal gradients are not as stable. The different hydrodynamical behaviours between the two different zones have significant consequences on the biogeochemistry: oxygen barely diffuses down to the hypolimnion in the FF whereas destratification occurs sporadically during the rainy season in the OW. Although we found the same range of POC in the FF and the OW (2.5-29 μmol L-1) and 20% more DOC at the bottom of OW than in the FF (229-878 μmol L-1), CO2 and CH4 concentrations were always significantly higher in the FF (CO2: 11-1412 μmol L-1, CH4: 0.001-1015 μmol L-1) than in the OW. On average, the CO2 concentrations were 30-40% higher in the FF than in the OW and the CH4 concentrations were three times higher in the FF than in the OW. The δ13C-POC and C:N values did not suggest substantial differences in the sources of OM between the FF and OW. At all stations, POC at the bottom has an isotopic signature slightly lighter than the terrestrial OM in the surrounding forest whereas the isotopic signature of surface POM would result from phytoplankton and methanotrophs. The vertical profiles of nitrogen compounds reveal that the main

Infrared absorption of CH{sub 3}OSO and CD{sub 3}OSO radicals produced upon photolysis of CH{sub 3}OS(O)Cl and CD{sub 3}OS(O)Cl in p-H{sub 2} matrices

Energy Technology Data Exchange (ETDEWEB)

Lee, Yu-Fang; Kong, Lin-Jun [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan (China); Lee, Yuan-Pern [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)

2012-03-28

Irradiation at 239 {+-} 20 nm of a p-H{sub 2} matrix containing methoxysulfinyl chloride, CH{sub 3}OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to {nu}{sub 1}, CH{sub 2} antisymmetric stretching), 2999.5 ({nu}{sub 2}, CH{sub 3} antisymmetric stretching), 2950.4 ({nu}{sub 3}, CH{sub 3} symmetric stretching), 1465.2 ({nu}{sub 4}, CH{sub 2} scissoring), 1452.0 ({nu}{sub 5}, CH{sub 3} deformation), 1417.8 ({nu}{sub 6}, CH{sub 3} umbrella), 1165.2 ({nu}{sub 7}, CH{sub 3} wagging), 1152.1 ({nu}{sub 8}, S=O stretching mixed with CH{sub 3} rocking), 1147.8 ({nu}{sub 9}, S=O stretching mixed with CH{sub 3} wagging), 989.7 ({nu}{sub 10}, C-O stretching), and 714.5 cm{sup -1} ({nu}{sub 11}, S-O stretching) modes of syn-CH{sub 3}OSO. When CD{sub 3}OS(O)Cl in a p-H{sub 2} matrix was used, lines at 2275.9 ({nu}{sub 1}), 2251.9 ({nu}{sub 2}), 2083.3 ({nu}{sub 3}), 1070.3 ({nu}{sub 4}), 1056.0 ({nu}{sub 5}), 1085.5 ({nu}{sub 6}), 1159.7 ({nu}{sub 7}), 920.1 ({nu}{sub 8}), 889.0 ({nu}{sub 9}), 976.9 ({nu}{sub 10}), and 688.9 ({nu}{sub 11}) cm{sup -1} appeared and are assigned to syn-CD{sub 3}OSO; the mode numbers correspond to those used for syn-CH{sub 3}OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86/aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH{sub 3}OSO near 2991, 2956, 1152, and 994 cm{sup -1} to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD{sub 3}OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H{sub 2} such that the Cl atom, produced via UV photodissociation of CH{sub 3}OS(O)Cl in situ, might escape from the original cage to yield isolated CH{sub 3}OSO