Hodnocení elektrochemických charakteristik tvářených hořčíkových slitin typu Mg-Al-Zn

OpenAIRE

Slouková, Karolína

2016-01-01

Cílem této diplomové práce je zhodnotit elektrochemické charakteristiky slitin hořčíku. Teoretická část se zabývá popisem vlastností hořčíku i jeho slitin a také jejich korozních charakteristik. V experimentální části jsou interpretovány výsledky měření korozní odolnosti dvou tvářených hořčíkových slitin. Jednalo se o slitiny AZ31 a AZ61, které byly podrobeny měření v Hankových roztocích s přídavkem iontů Ca2+ a Mg2+ (SBF+) a bez jejich přídavku (SBF). Teplota roztoku během měření byla zvolen...

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...

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

Science.gov (United States)

Guérin, Frédéric; Leon, Juan

2015-04-01

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

Enhanced Selectivity and Uptake Capacity of CO2 and Toluene Adsorption in Co0.5 M0.33 MoS4 (M= Sb or Y) Chalcogels by Impregnated Metal Salts

KAUST Repository

Adhiam, Fatima Abdullah Ahmed

2017-11-17

The synthesis of metal chalcogenide aerogels Co0.5M0.33MoS4 (M= Sb or Y) by the sol-gel method is reported. In this system, the building blocks [MoS4]2− chelated with Co2+ and (Sb3+) or (Y3+) salts in nonaqueous solvents forming amorphous networks with a gel property. The chalcogels obtained after supercritical drying have BET surface areas of 176 m2 g−1 (Co0.5Sb0.33MoS4) and 145 m2 g−1 (Co0.5Y0.33MoS4). Electron microscopy and physisorption studies reveal that the new materials are porous with wide pore size distribution and average pore width of 16 nm. These chalcogels show higher adsorption capacity of toluene vapor (Co0.5Sb0.33MoS4: 387 mg g−1) and (Co0.5Y0.33MoS4: 304 mg g−1) over cyclohexane vapor and high selectivity of CO2 over CH4 or H2, Co0.5Sb0.33MoS4 (CO2/H2: 80 and CO2/CH4: 21), Co0.5Y0.33MoS4 (CO2/H2: 27 and CO2/CH4: 15). We also demonstrated that the impregnation of various metal species like Li+, Mg2+, and Ni2+ significantly enhanced the uptake capacity and selectivity of toluene and CO2 adsorptions in the chacogels.

Study on the equilibrium in the MBr2-CH3OH-H2O system (M = Sr2+, Ba2+) at 25 0C

International Nuclear Information System (INIS)

Zlateva, I.; Stoev, M.

1985-01-01

The dehydration processes in the three-component system MBr 2 -CH 3 OH-H 2 O (M = Sr 2+ , Ba 2+ ) have been studied at 25 0 C by physio-chemical analyses. Crystallization fields for the lower crystal hydrates SrBr 2 x H 2 O and BaBr 2 x H 2 O have been found. The solubility curves exhibit complex-formation processes. The dehydration and solvation processes in three-component system such as MBr 2 -CH 3 OH-H 2 O at 25 0 C with M = Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ have been discussed in general terms. (author)

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.

Large CO2 and CH4 release from a flooded formerly drained fen

Science.gov (United States)

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

2016-12-01

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

The rate of charge tunneling is insensitive to polar terminal groups in self-assembled monolayers in Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn junctions.

Science.gov (United States)

Yoon, Hyo Jae; Bowers, Carleen M; Baghbanzadeh, Mostafa; Whitesides, George M

2014-01-08

This paper describes a physical-organic study of the effect of uncharged, polar, functional groups on the rate of charge transport by tunneling across self-assembled monolayer (SAM)-based large-area junctions of the form Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn. Here Ag(TS) is a template-stripped silver substrate, -M- and -T are "middle" and "terminal" functional groups, and EGaIn is eutectic gallium-indium alloy. Twelve uncharged polar groups (-T = CN, CO2CH3, CF3, OCH3, N(CH3)2, CON(CH3)2, SCH3, SO2CH3, Br, P(O)(OEt)2, NHCOCH3, OSi(OCH3)3), having permanent dipole moments in the range 0.5 < μ < 4.5, were incorporated into the SAM. A comparison of the electrical characteristics of these junctions with those of junctions formed from n-alkanethiolates led to the conclusion that the rates of charge tunneling are insensitive to the replacement of terminal alkyl groups with the terminal polar groups in this set. The current densities measured in this work suggest that the tunneling decay parameter and injection current for SAMs terminated in nonpolar n-alkyl groups, and polar groups selected from common polar organic groups, are statistically indistinguishable.

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

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

CO2 Reforming of CH4 by Atmospheric Pressure Abnormal Glow Plasma

International Nuclear Information System (INIS)

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

2006-01-01

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

Field measurements and modeling to resolve m2 to km2 CH4 emissions for a complex urban source: An Indiana landfill study

Directory of Open Access Journals (Sweden)

Maria Obiminda L. Cambaliza

2017-07-01

Full Text Available Large spatial and temporal uncertainties for landfill CH4 emissions remain unresolved by short-term field campaigns and historic greenhouse gas (GHG inventory models. Using four field methods (aircraft-based mass balance, tracer correlation, vertical radial plume mapping, static chambers and a new field-validated process-based model (California Landfill Methane Inventory Model, CALMIM 5.4, we investigated the total CH4 emissions from a central Indiana landfill as well as the partitioned emissions inclusive of methanotrophic oxidation for the various cover soils at the site. We observed close agreement between whole site emissions derived from the tracer correlation (8 to 13 mol s–1 and the aircraft mass balance approaches (7 and 17 mol s–1 that were statistically indistinguishable from the modeling result (12 ± 2 mol s–1 inclusive of oxidation. Our model calculations indicated that approximately 90% of the annual average CH4 emissions (11 ± 1 mol s–1; 2200 ± 250 g m–2 d–1 derived from the small daily operational area. Characterized by a thin overnight soil cover directly overlying a thick sequence of older methanogenic waste without biogas recovery, this area constitutes only 2% of the 0.7 km2 total waste footprint area. Because this Indiana landfill is an upwind source for Indianapolis, USA, the resolution of m2 to km2 scale emissions at various temporal scales contributes to improved regional inventories relevant for addressing GHG mitigation strategies. Finally, our comparison of measured to reported CH4 emissions under the US EPA National GHG Reporting program suggests the need to revisit the current IPCC (2006 GHG inventory methodology based on CH4 generation modeling. The reasonable prediction of emissions at individual U.S. landfills requires incorporation of both cover-specific landfill climate modeling (e.g., soil temperature/moisture variability over a typical annual cycle driving CH4 transport and oxidation rates as

Livestock induces strong spatial heterogeneity of soil CO2, N2O and CH4 emissions within a semi-arid sylvo-pastoral landscape in West Africa

Institute of Scientific and Technical Information of China (English)

Mohamed H ASSOUMA; Dominique SER(C)A; Frédéric GU(E)RIN; Vincent BLANFORT; Philippe LECOMTE; Ibra TOUR(E); Alexandre ICKOWICZ

2017-01-01

Greenhouse gas (GHG) emissions from the surface soils and surface water receiving animal excreta may be important components of the GHG balance of terrestrial ecosystems,but the associated processes are poorly documented in tropical environments,especially in tropical arid and semi-arid areas.A typical sylvo-pastoral landscape in the semi-arid zone of Senegal,West Africa,was investigated in this study.The study area (706 km2 of managed pastoral land) was a circular zone with a radius of 15 km centered on a borehole used to water livestock.The landscape supports a stocking rate ranging from 0.11 to 0.39 tropical livestock units per hectare depending on the seasonal movements of the livestock.Six landscape units were investigated (land in the vicinity of the borehole,natural ponds,natural rangelands,forest plantations,settlements,and enclosed plots).Carbon dioxide (CO2),nitrous oxide (N2O) and methane (CH4) fluxes were measured with static chambers set up at 13 sites covering the six landscape units,and the 13 sites are assumed to be representative of the spatial heterogeneity of the emissions.A total of 216 fluxes were measured during the one-year study period (May 2014 to April 2015).At the landscape level,soits and surface water emitted an average 19.8 t C-CO2 eq/(hm2·a) (CO2:82％,N2O:15％,and CH4:3％),but detailed results revealed notable spatial heterogeneity of GHG emissions.CO2 fluxes ranged from 1148.2 (±91.6) mg/(m2·d) in rangelands to 97,980.2 (±14,861.7) mg/(m2·d) in surface water in the vicinity of the borehole.N2O fluxes ranged from 0.6 (±0.1) mg/(m2·d) in forest plantations to 22.6 (±10.8) mg/(m2·d) in the vicinity of the borehole.CH4 fluxes ranged from-3.2 (±0.3) mg/(m2·d) in forest plantations to 8788.5 (±2295.9) mg/(m2·d) from surface water in the vicinity of the borehole.This study identified GHG emission "hot spots" in the landscape.Emissions from the surface soilts were significantly higher in the landscape units most frequently

Magnesium replacement in formaldehyde: Theoretical rovibrational analysis of X ∼ 3B1 MgCH2

Science.gov (United States)

Bassett, Matthew K.; Fortenberry, Ryan C.

2018-02-01

A full, anharmonic set of fundamental vibrational frequencies as well as spectrosocpic constants are provided at high-level for X ∼ 3B1 MgCH2 for the first time. The present data are in line with previous computational and Ar-matrix results, but the anharmonic data show that two brightest frequencies, ν4 and ν5 , are nearly coincident with one another at 560 cm-1. Hence, this area is the best spectral region to search for signatures of this molecule. The rotational constants are also provided indicating a near-prolate rotational progression which should aid in microwave/millimeter-wave analysis of this molecule. Magnesium is known to be a significant component of the Earth, and molecules containing it may be more common in the interstellar medium/circumstellar media than previously thought. More spectral characterization of such molecules like MgCH2 should be undertaken, and this work is a step in that direction.

Impact of raw pig slurry and pig farming practices on physicochemical parameters and on atmospheric N2O and CH 4 emissions of tropical soils, Uvéa Island (South Pacific).

Science.gov (United States)

Roth, E; Gunkel-Grillon, P; Joly, L; Thomas, X; Decarpenterie, T; Mappe-Fogaing, I; Laporte-Magoni, C; Dumelié, N; Durry, G

2014-09-01

Emissions of CH4 and N2O related to private pig farming under a tropical climate in Uvéa Island were studied in this paper. Physicochemical soil parameters such as nitrate, nitrite, ammonium, Kjeldahl nitrogen, total organic carbon, pH and moisture were measured. Gaseous soil emissions as well as physicochemical parameters were compared in two private pig farming strategies encountered on this island on two different soils (calcareous and ferralitic) in order to determine the best pig farming management: in small concrete pens or in large land pens. Ammonium levels were higher in control areas while nitrate and nitrite levels were higher in soils with pig slurry inputs, indicating that nitrification was the predominant process related to N2O emissions. Nitrate contents in soils near concrete pens were important (≥ 55 μg N/g) and can thus be a threat for the groundwater. For both pig farming strategies, N2O and CH4 fluxes can reach high levels up to 1 mg N/m(2)/h and 1 mg C/m(2)/h, respectively. CH4 emissions near concrete pens were very high (≥ 10.4 mg C/m(2)/h). Former land pens converted into agricultural land recover low N2O emission rates (≤ 0.03 mg N/m(2)/h), and methane uptake dominates. N2O emissions were related to nitrate content whereas CH4 emissions were found to be moisture dependent. As a result relating to the physicochemical parameters as well as to the gaseous emissions, we demonstrate that pig farming in large land pens is the best strategy for sustainable family pig breeding in Uvéa Islands and therefore in similar small tropical islands.

CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

Science.gov (United States)

Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

2015-07-16

The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The

Isopiestic Investigation of the Osmotic and Activity Coefficients of {yMgCl2 + (1 - y)MgSO4}(aq) and the Osmotic Coefficients of Na2SO4.MgSO4(aq) at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Miladinovic, J; Ninkovic, R; Todorovic, M; Rard, J A

2007-06-06

Isopiestic vapor pressure measurements were made for {l_brace}yMgCl{sub 2} + (1-y)MgSO{sub 4}{r_brace}(aq) solutions with MgCl{sub 2} ionic strength fractions of y = 0, 0.1997, 0.3989, 0.5992, 0.8008, and (1) at the temperature 298.15 K, using KCl(aq) as the reference standard. These measurements for the mixtures cover the ionic strength range I = 0.9794 to 9.4318 mol {center_dot} kg{sup -1}. In addition, isopiestic measurements were made with NaCl(aq) as reference standard for mixtures of {l_brace}xNa{sub 2}SO{sub 4} + (1-x)MgSO{sub 4}{r_brace}(aq) with the molality fraction x = 0.50000 that correspond to solutions of the evaporite mineral bloedite (astrakanite), Na{sub 2}Mg(SO{sub 4}){sub 2} {center_dot} 4H{sub 2}O(cr). The total molalities, m{sub T} = m(Na{sub 2}SO{sub 4}) + m(MgSO{sub 4}), range from m{sub T} = 1.4479 to 4.4312 mol {center_dot} kg{sup -1} (I = 5.0677 to 15.509 mol {center_dot} kg{sup -1}), where the uppermost concentration is the highest oversaturation molality that could be achieved by isothermal evaporation of the solvent at 298.15 K. The parameters of an extended ion-interaction (Pitzer) model for MgCl2(aq) at 298.15 K, which were required for an analysis of the {l_brace}yMgCl{sub 2} + (1-y)MgSO{sub 4}{r_brace}(aq) mixture results, were evaluated up to I = 12.025 mol {center_dot} kg{sup -1} from published isopiestic data together with the six new osmotic coefficients obtained in this study. Osmotic coefficients of {l_brace}yMgCl{sub 2} + (1-y)MgSO{sub 4}{r_brace}(aq) solutions from the present study, along with critically-assessed values from previous studies, were used to evaluate the mixing parameters of the extended ion-interaction model.

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

Science.gov (United States)

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

2014-01-01

Permafrost soils store over half of global soil carbon (C), and northern frozen peatlands store about 10% of global permafrost C. With thaw, inundation of high latitude lowland peatlands typically increases the surface-atmosphere flux of methane (CH4), a potent greenhouse gas. To examine the effects of lowland permafrost thaw over millennial timescales, we measured carbon dioxide (CO2) and CH4 exchange along sites that constitute a ~1000 yr thaw chronosequence of thermokarst collapse bogs and adjacent fen locations at Innoko Flats Wildlife Refuge in western Alaska. Peak CH4exchange in July (123 ± 71 mg CH4–C m−2 d−1) was observed in features that have been thawed for 30 to 70 (peatlands, particularly those developed on poorly drained mineral substrates, are a key locus of elevated CH4 emission to the atmosphere that must be considered for a complete understanding of high latitude CH4 dynamics.

Molecular Simulations and Theoretical Predictions for Adsorption and Diffusion of CH{sub 4}/H{sub 2} and CO{sub 2}/CH{sub 4} Mixtures in ZIFs

Energy Technology Data Exchange (ETDEWEB)

Liu, Jinchen; Keskin, Seda; Sholl, David S; Johnson, J. Karl

2011-05-01

Adsorption and diffusion of CO{sub 2}/CH{sub 4} and CH{sub 4}/H{sub 2} mixtures were computed in zeolite imidazolate frameworks (ZIFs), ZIF-68 and ZIF-70, using atomically detailed simulations. Adsorption selectivity, diffusion selectivity, and membrane selectivity of ZIFs were calculated based on the results of atomistic simulations. Mixture adsorption isotherms predicted by the ideal adsorbed solution theory agree well with the results of molecular simulations for both ZIFs. Mixture diffusivity calculations indicate that diffusion of CH{sub 4} is increased with increasing concentration of H{sub 2} in the CH{sub 4}/H{sub 2} mixture, while the diffusivity of H{sub 2} decreases with increasing CH{sub 4} concentration. In contrast, the diffusivity of CH{sub 4} is essentially independent of the concentration of CO{sub 2} in the CO{sub 2}/CH{sub 4} mixture, while CO{sub 2} diffusivity decreases with increased CH{sub 4} loading, even though the diffusivity of CH{sub 4} is substantially larger than that of CO{sub 2}. This unusual behavior can be explained in terms of differences in adsorption site preferences due to charge–quadrupole interactions.

The effects of CO addition on the autoignition of H-2, CH4 and CH4/H-2 fuels at high pressure in an RCM

NARCIS (Netherlands)

Gersen, Sander; Darmeveil, Harry; Levinsky, Howard

2012-01-01

Autoignition delay times of stoichiometric and fuel-lean (phi = 0.5) H-2, H-2/CO, CH4, CH4/CO, CH4/H-2 and CH4/CO/H-2 mixtures have been measured in an Rapid Compression Machine at pressures ranging from 20 to 80 bar and in the temperature range 900-1100K. The effects of CO addition on the ignition

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

NARCIS (Netherlands)

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

1989-01-01

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

The ternary system K2SO4MgSO4CaSO4

Science.gov (United States)

Rowe, J.J.; Morey, G.W.; Silber, C.C.

1967-01-01

Melting and subsolidus relations in the system K2SO4MgSO4CaSO4 were studied using heating-cooling curves, differential thermal analysis, optics, X-ray diffraction at room and high temperatures and by quenching techniques. Previous investigators were unable to study the binary MgSO4CaSO4 system and the adjacent area in the ternary system because of the decomposition of MgSO4 and CaSO4 at high temperatures. This problem was partly overcome by a novel sealed-tube quenching method, by hydrothermal synthesis, and by long-time heating in the solidus. As a result of this study, we found: (1) a new compound, CaSO4??3MgSO4 (m.p. 1201??C) with a field extending into the ternary system; (2) a high temperature form of MgSO4 with a sluggishly reversible inversion. An X-ray diffraction pattern for this polymorphic form is given; (3) the inversion of ??-CaSO4 (anhydrite) to ??-CaSO4 at 1195??C, in agreement with grahmann; (1) (4) the melting point of MgSO4 is 1136??C and that of CaSO4 is 1462??C (using sealed tube methods to prevent decomposition of the sulphates); (5) calcium langbeinite (K2SO4??2CaSO4) is the only compound in the K2SO4CaSO4 binary system. This resolved discrepancies in the results of previous investigators; (6) a continuous solid solution series between congruently melting K2SOP4??2MgSO4 (langbeinite) and incongruently melting K2SO4??2CaSO4 (calcium langbeinite); (7) the liquidus in the ternary system consists of primary phase fields of K2SO4, MgSO4, CaSO4, langbeinite-calcium langbeinite solid solution, and CaSO4??3MgSO4. The CaSO4 field extends over a large portion of the system. Previously reported fields for the compounds (K2SO4??MgSO4??nCaSO4), K2SO4??3CaSO4 and K2SO4??CaSO4 were not found; (8) a minimum in the ternary system at: 740??C, 25% MgSO4, 6% CaSO4, 69% K2SO4; and ternary eutectics at 882??C, 49% MgSO4, 19% CaSO4, 32% K2SO4; and 880??, 67??5% MgSO4, 5% CaSO4, 27??5% K2SO4. ?? 1967.

Kinetics of the reactions H+C2H4->C2H5, H+C2H5->2CH3 and CH3+C2H5->products studies by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Sillesen, A.; Ratajczak, E.; Pagsberg, P.

1993-01-01

Formation of methyl radicals via the consecutive reactions H+C2H4+M-->C2H5+M (1) and H+C2H5-->CH3+CH3 (2a) was initiated by pulse radiolysis of 10-100 mbar H-2 in the presence of ethylene. The kinetics of CH3 Were studied by monitoring the transient infrared absorption at the Q(3, 3) line of the ...

Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C2H2/CO2 and C2H2/CH4 separation performance.

Science.gov (United States)

Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Qu, Peng; Zhai, Quan-Guo

2018-02-20

A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH 4 (120.6) selectivity among all the reported MOFs at room temperature.

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

Science.gov (United States)

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

2009-03-26

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

Luminescence Properties of Self-Activated Mm(VO4)2 (M = Mg, Ca, Sr, and Ba) Phosphors Synthesized by Solid-State Reaction Method.

Science.gov (United States)

Min, Xin; Huang, Zhaohui; Fang, Minghao; Liu, Yan'gai; Tang, Chao; Wu, Xiaowen

2016-04-01

In this paper, M3(VO4)2 (M = Mg, Ca, Sr, and Ba) self-activated phosphors were prepared by a solid-state reaction method at 1,000 °C for 5 h. The phase formation and micrographs were analyzed by X-ray diffraction and scanning electron microscopy. The Ca3(VO4)2 phosphor does not show any emission peaks under excitation with ultraviolet (UV) light. However, the M3(VO4)2 (M = Mg, Sr, and Ba) samples are effectively excited by UV light chips ranging from 200 nm to 400 nm and exhibit broad emission bands due to the charge transfer from the oxygen 2p orbital to the vacant 3d orbital of the vanadium in the VO4. The color of these phosphors changes from yellow to light blue via blue-green with increasing ionic radius from Mg to Sr to Ba. The luminescence lifetimes and quantum yield decrease with the increasing unit cell volume and V-V distance, in the order of Mg3(VO4)2 to Sr3(VO4)2 to Ba3(VO4)2. The emission intensity decreases with the increase of temperatures, but presents no color shift. This confirms that these self-activated M3(VO4)2 phosphors can be suggested as candidates of the single-phase phosphors for light using UV light emitting diodes (LEDs).

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.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets).

Science.gov (United States)

Holm, N G; Oze, C; Mousis, O; Waite, J H; Guilbert-Lepoutre, A

2015-07-01

Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds.

CO2/CH4 Separation via Polymeric Blend Membrane

Directory of Open Access Journals (Sweden)

H. Sanaeepur

2013-01-01

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

Soil CO2, CH4 and N2O effluxes and concentrations in soil profiles down to 15.5m depth in eucalypt plantations under contrasted rainfall regimes

Science.gov (United States)

Germon, A.; Nouvellon, Y.; Christophe, J.; Chapuis-Lardy, L.; Robin, A.; Rosolem, C. A.; Gonçalves, J. L. D. M.; Guerrini, I. A.; Laclau, J. P.

2017-12-01

Silvicultural practices in planted forests affect the fluxes of greenhouse gases at the soil surface and the major factors driving greenhouse gas production in forest soils (substrate supply, temperature, water content,…) vary with soil depth. Our study aimed to assess the consequences of drought on the temporal variability of CO2, CH4 and N2O fluxes throughout very deep soil profiles in Eucalyptus grandis plantations 3 months before the harvest then in coppice, the first 18 months after clear-cutting. Two treatments were compared: one with 37% of throughfall excluded by plastic sheets (TE), and one without rainfall exclusion (WE). Measurements of soil CO2 efflux were made every two weeks for 30 months using a closed-path Li8100 system in both treatment. Every two weeks for 21 months, CO2, CH4 and N2O surface effluxes were measured using the closed-chamber method and concentrations in the soil were measured at 7 depths down to 15.5 m in both TE and WE. At most measurement dates, soil CO2 efflux were significantly higher in TE than in WE. Across the two treatments and the measurement dates, CO2 concentrations increased from 4446 ± 2188 ppm at 10 cm deep to 15622 ± 3523 ppm at 15.5 m, CH4 concentrations increased from 0.41 ± 0.17 ppm at 10 cm deep to 0.77 ± 0.24 ppm at 15.5 m and N2O concentrations remained roughly constant and were on average 478 ± 55 ppb between soil surface and 15.5 m deep. CO2 and N2O concentrations were on average 20.7 and 7.6% lower in TE than in WE, respectively, across the sampling depths. However, CH4 concentrations in TE were on average 44.4% higher than in WE, throughout the soil profile. Those results suggest that extended drought periods might reduce the production of CO2 and N2O but increase the accumulation of CH4 in eucalypt plantations established in deep tropical soils. Very deep tropical soils cover huge areas worldwide and improving our understanding of the spatiotemporal dynamics of gas concentrations in deep soil layers

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

Science.gov (United States)

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

2013-12-01

Approximately 14% of the Alaskan North Slope is covered in lakes of various sizes and depths. Diffusive carbon emissions (CH4 and CO2) from these lakes offset the tundra sink by ~20 %, but the offset would substantially increase if ebullitive CH4 emissions were also considered. Ultimately, arctic lake CH4 emissions are not insignificant in the global CH4 budget and their contribution is bound to increase due to impacts from climate change. Here we present high resolution CH4 emission data as measured via eddy covariance and a Los Gatos gas analyzer during the ice free period from Toolik Lake, a deep (20 m) Arctic lake located on the Alaskan North Slope, over the last few summers. Emissions are relatively low (Gatos gas analyzer. Thus, having both the flux and the CH4 gradient across the air-water interface measured directly, we can calculate k and investigate the processes influencing CH4 gas exchange in this lake. Preliminary results indicate that there are two regimes in wind speed that impact k - one at low wind speeds up to ~5 m s-1 and another at higher wind speeds (max ~10 m s-1). The differential wind speeds during night and day may compound the effect of convective mixing and cause the diurnal variation in observed fluxes.

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...

Defect kinetics in spinels: Long-time simulations of MgAl2O4, MgGa2O4, and MgIn2O4

International Nuclear Information System (INIS)

Uberuaga, B. P.; Voter, A. F.; Sickafus, K. E.; Bacorisen, D.; Smith, Roger; Ball, J. A.; Grimes, R. W.

2007-01-01

Building upon work in which we examined defect production and stability in spinels, we now turn to defect kinetics. Using temperature accelerated dynamics (TAD), we characterize the kinetics of defects in three spinel oxides: magnesium aluminate MgAl 2 O 4 , magnesium gallate MgGa 2 O 4 , and magnesium indate MgIn 2 O 4 . These materials have varying tendencies to disorder on the cation sublattices. In order to understand chemical composition effects, we first examine defect kinetics in perfectly ordered, or normal, spinels, focusing on point defects on each sublattice. We then examine the role that cation disorder has on defect mobility. Using TAD, we find that disorder creates local environments which strongly trap point defects, effectively reducing their mobility. We explore the consequences of this trapping via kinetic Monte Carlo (KMC) simulations on the oxygen vacancy (V O ) in MgGa 2 O 4 , finding that V O mobility is directly related to the degree of inversion in the system

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

NARCIS (Netherlands)

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

1999-01-01

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

Structural features of AgCaCdMg2(PO4)3 and AgCd2Mg2(PO4)3, two new compounds with the alluaudite-type structure, and their catalytic activity in butan-2-ol conversion

International Nuclear Information System (INIS)

Kacimi, Mohammed; Ziyad, Mahfoud; Hatert, Frederic

2005-01-01

AgCaCdMg 2 (PO 4 ) 3 and AgCd 2 Mg 2 (PO 4 ) 3 , two new compounds with the alluaudite-type structure, were synthesized by a solid state reaction in air at 750 deg. C. The X-ray powder diffraction pattern of AgCaCdMg 2 (PO 4 ) 3 indicates the presence of small amounts of (Ca, Mg) 3 (PO 4 ) 2 with the whitlockite structure, as impurity, whereas AgCd 2 Mg 2 (PO 4 ) 3 is constituted by pure alluaudite. The Rietveld refinements of the X-ray powder diffraction patterns indicate an ordered cationic distribution for AgCd 2 Mg 2 (PO 4 ) 3 , with Ag on A(2)', Cd on A(1) and M(1), and Mg on M(2), whereas a disordered distribution of Cd and Ca between the A(1) and M(1) sites is observed for AgCaCdMg 2 (PO 4 ) 3 . The catalytic properties of these compounds has been measured in reaction of butan-2-ol dehydrogenation. In the absence of oxygen, both samples exhibit poor dehydrogenation activity. All samples displayed no dehydration activity. Introduction of oxygen into the feed changed totally the catalytic behavior of the catalysts. The production of methyl ethyl ketone increases with time on stream and the reaction temperature. AgCaCdMg 2 (PO 4 ) 3 is more efficient than AgCd 2 Mg 2 (PO 4 ) 3

A Temperature Window for the Synthesis of Single-Walled Carbon Nanotubes by Catalytic Chemical Vapor Deposition of CH4over Mo2-Fe10/MgO Catalyst

Directory of Open Access Journals (Sweden)

Yu Ouyang

2009-01-01

Full Text Available Abstract A temperature window for the synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of CH4over Mo2-Fe10/MgO catalyst has been studied by Raman spectroscopy. The results showed that when the temperature is lower than 750 °C, there were few SWCNTs formed, and when the temperature is higher than 950 °C, mass amorphous carbons were formed in the SWCNTs bundles due to the self-decomposition of CH4. The temperature window of SWCNTs efficient growth is between 800 and 950 °C, and the optimum growth temperature is about 900 °C. These results were supported by transmission electron microscope images of samples formed under different temperatures. The temperature window is important for large-scale production of SWCNTs by catalytic chemical vapor deposition method.

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.

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO2 and CH4 Exchange Responds to Changes in Temperature and Precipitation

Science.gov (United States)

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.; Arora, B.; Torn, M. S.

2017-12-01

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO2 and CH4 exchange. Here we test hypotheses in ecosys for topographic controls on CO2 and CH4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO2 influxes and CH4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) than in higher (rims) within LCPs and FCPs. Spatially aggregated CO2 and CH4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52-56 g C m-2 yr-1) and CH4 sources (4-6 g C m-2 yr-1), and higher features as near C neutral (-2-15 g C m-2 yr-1) and CH4 neutral (0.0-0.1 g C m-2 yr-1). Much of the spatial and temporal variations in CO2 and CH4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.

A randomized comparison of daunorubicin 90 mg/m2 vs 60 mg/m2 in AML induction

DEFF Research Database (Denmark)

Burnett, A. K.; Russell, N. H.; Hills, R. K.

2015-01-01

Modifying induction therapy in acute myeloid leukemia (AML) may improve the remission rate and reduce the risk of relapse, thereby improving survival. Escalation of the daunorubicin dose to 90 mg/m(2) has shown benefit for some patient subgroups when compared with a dose of 45 mg/m(2), and has been...... = .15). In an exploratory subgroup analysis, there was no subgroup that showed significant benefit, although there was a significant interaction by FLT3 ITD mutation. This trial is registered at http://www.isrctn.com as #ISRCTN55675535....

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.

Rational design of organic superconductors through the use of the large, discrete molecular anions M(CF3)4-(M = Cu, Ag, Au) and SO3CF2CH2SF5-

International Nuclear Information System (INIS)

Schlueter, J.A.; Geiser, U.; Williams, J.M.

1996-01-01

A new approach to synthesis of organic superconductors has recently been pioneered which involves the use of large discrete molecular anions as the charge-compensating entities in these charge transfer salts. The organic electron-donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) has been electrocrystallized with the novel organometallic M(CF 3 ) 4 - (M=Cu, Ag, Au) anions in a variety of 1,1,2-trihaloethane solvents. Over 20 organic superconductors have been synthesized which can be described by (ET) 2 M(CF 3 ) 4 (1,1,2- trihaloethane). These solvated salts are shown to have highly anisotropic physical properties which can be tuned via modifications of each of their three molecular components: ET electron donor molecule, M(CF 3 ) 4 - anion, and neutral 1,1,2- trihaloethane solvent molecule. Superconductivity has also been observed in an ET salt containing the discrete SF 5 CH 2 CF 2 SO 3 - anion with onset temperature near 5.2 K

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.

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...

[Effect of carbon substrate concentration on N2, N2O, NO, CO2, and CH4 emissions from a paddy soil in anaerobic condition].

Science.gov (United States)

Chen, Nuo; Liao, Ting-ting; Wang, Rui; Zheng, Xun-hua; Hu, Rong-gui; Butterbach-Bahl, Klaus

2014-09-01

Understanding the effects of carbon and nitrogen substrates concentrations on the emissions of denitrification gases including nitrogen (N2) , nitrous oxide (N2O) and nitric oxide (NO), carbon dioxide (CO2) and methane (CH4) from anaerobic paddy soils is believed to be helpful for development of greenhouse gas mitigation strategies. Moreover, understanding the quantitative dependence of denitrification products compositions on carbon substrate concentration could provide some key parameters or parameterization scheme for developing process-oriented model(s) of nitrogen transformation. Using a silt loam soil collected from a paddy field, we investigated the influence of carbon substrate concentration on the emissions of the denitrification gases, CO2 and CH4 from anaerobically incubated soils by setting two treatments: control (CK) with initial soil nitrate and dissolved organic carbon (DOC) concentrations of ~ 50 mg.kg-1 and -28 mg kg-1 , respectively; and DOC added (C + ) with initial soil nitrate and DOC concentrations of ~50 mg.kg-1 and ~300 mg.kg-1 , respectively. The emissions of denitrification gases, CO2 and CH4, as well as concentrations of carbon and nitrogen substrates for each treatment were dynamically measured, using the gas-flow-soil-core technique and a paralleling substrate monitoring system. The results showed that CH4 emission was not observed in CK treatment while observed in C treatment. Aggregate emission of greenhouse gases for C + treatment was significantly higher comparing with the CK treatment (P emissions in total nitrogen gases emissions were approximately 9% , 35% and 56% for CK treatment, respectively; and approximately 31% , 50% and 19% for C+ treatment, respectively, with significant differences between these two treatments (P carbon substrate concentrations can significantly change the composition of nitrogen gas emissions. The results also implicated that organic fertilizer should not be applied to nitrate-rich paddy soils prior to

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

Fracture toughness of MgCr2O4-ZrO2 composities

International Nuclear Information System (INIS)

Singh, J.P.

1985-01-01

The effect of unstabilized ZrO 2 inclusions on the fracture surface energy of MgCr 2 O 4 was studied as a function of ZrO 2 content. It was observed that fracture surface energy increases with increasing ZrO 2 content, and reaches the maximum value of 24.5 j/m 2 at 16.5 vol% ZrO 2 . This represents an approx. = fourhold increase in the fracture surface energy of Mg 2 O 4 as a result of ZrO 2 inclusions. It is proposed that this improvement results from the energy absorbed by the microcracks formed in the MgCr 2 O 4 matrix as a result of the tetragonal → monoclinic phase transormation of ZrO 2 and the associated volume expansion

Interannual variability in CO2 and CH4 exchange in a brackish tidal marsh in Northern California

Science.gov (United States)

Knox, S. H.; Windham-Myers, L.; Anderson, F. E.; Bergamaschi, B. A.

2017-12-01

Carbon (C) cycling in coastal wetlands is difficult to measure and model due to extremely dynamic atmospheric and hydrologic fluxes, as well as sensitivities to dynamic land- and ocean-based drivers. To date, few studies have begun continuous measurements of net ecosystem CO2 exchange (NEE) in these systems, and as such our understanding of the key drivers of NEE in coastal wetlands remain poorly understood. Recent eddy covariance measurements of NEE in these environments show considerable variability both within and across sites, with daily CO2 uptake and annual net CO2 budgets varying by nearly an order of magnitude between years and across locations. Furthermore, measurements of CH4 fluxes in these systems are even more limited, despite the potential for CH4 emissions from brackish and freshwater coastal wetlands. Here we present 3 years of near-continuous eddy covariance measurements of CO2 and CH4 fluxes from a brackish tidal marsh in Northern California and explore the drivers of interannual variability in CO2 and CH4 exchange. CO2 fluxes showed significant interannual variability; net CO2 uptake was near-zero in 2014 (6 ± 26 g C-CO2 m-2 yr-1), while much greater uptake was observed in 2015 and 2016 (209 ± 27 g C- CO2 m-2 yr-1 and 243 ± 26 g C-CO2 m-2 yr-1, respectively). Conversely, annual CH4 emissions were small and consistent across years, with the wetland emitting on average 1 ± 0.1 g C-CH4 m-2 yr-1. With respect to the net atmospheric GHG budget (assuming a sustained global warming potential (SGWP) of 45, expressed in units of CO2 equivalents), the wetland was near neutral in 2014, but a net GHG sink of 706 ± 105 g CO2 eq m-2 yr-1 and 836 ± 83 g CO2 eq m-2 yr-1 in 2015 and 2016, respectively. The large interannual variability in CO2 exchange was driven by notable year-to-year differences in temperature and precipitation as California experienced a severe drought and record high temperatures from 2012 to 2015. The large interannual variability in

DFT study on oxidation of HS(CH2) m SH ( m = 1-8) in oxidative desulfurization

Science.gov (United States)

Song, Y. Z.; Song, J. J.; Zhao, T. T.; Chen, C. Y.; He, M.; Du, J.

2016-06-01

Density functional theory was employed for calculation of HS(CH2) m SH ( m = 1-8) and its derivatives at B3LYP method at 6-31++g ( d, p) level. Using eigenvalues of LUMO and HOMO for HS(CH2) m SH, the standard electrode potentials were estimated by a stepwise multiple regression techniques (MLR), and obtained as E° = 1.500 + 7.167 × 10-3 HOMO-0.229 LUMO with high correlation coefficients of 0.973 and F values of 43.973.

Co-hydrothermal synthesis of LiMn_2_3_/_2_4Mg_1_/_2_4PO_4·LiAlO_2/C nano-hybrid cathode material with enhanced electrochemical performance for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Jun; Luo, Shaohua; Chang, Longjiao; Hao, Aimin; Wang, Zhiyuan; Liu, Yanguo; Xu, Qian; Wang, Qing; Zhang, Yahui

2017-01-01

Highlights: • A co-hydrothermal approach to synthesize LiMn_2_3_/_2_4Mg_1_/_2_4PO_4·LiAlO_2/C composite material in water/PEG system is present. • The Mn_1_-_xMg_xPO_4 precursor is prepared by precipitation reaction. • Co-modified with Mg"2"+ doping and LiAlO_2 compositing strategies play an important role in improving the electronic conductivity and facilitating the diffusion of lithium ion. • LiMn_2_3_/_2_4Mg_1_/_2_4PO_4·LiAlO_2/C composite material exhibits a high specific discharge capacity of 151.8 mAh/g at 0.05C. - Abstract: LiMn_2_3_/_2_4Mg_1_/_2_4PO_4·LiAlO_2/C is synthesized by a co-hydrothermal method in water/PEG system using Li_2CO_3, AAO and Mn_1_-_xMg_xPO_4 as raw material. The electronic structure and micromorphology of multi-component compound LiMn_1_-_xMg_xPO_4/C (x = 0, 1/24, 1/12, 1/6) and nano-hybrid LiMn_2_3_/_2_4Mg_1_/_2_4PO_4·LiAlO_2/C cathode materials are studied by first-principles calculation and experimental research including XRD, SEM, TEM. The calculated band gap of LiMn_2_3_/_2_4Mg_1_/_2_4PO_4/C is 2.296 eV, which is lower than other percentages Mg"2"+ doping samples. Electrochemical tests exhibit LiMn_2_3_/_2_4Mg_1_/_2_4PO_4/C has better cycling performance and rate capability than other contents Mg"2"+ doping samples with the discharge capacity of 143.5 mAh/g, 141.5 mAh/g, 139.2 mAh/g and 136.3 mAh/g at 0.05C, 0.1C, 0.5C and 1C in order. After compositing and preparation of LiMn_2_3_/_2_4Mg_1_/_2_4PO_4·LiAlO_2/C composite material by co-hydrothermal route, the initial discharge capacity reaches up to 151.8 mAh/g, which suggests that co-modified with Mg"2"+ doping and LiAlO_2 compositing material can improve the electronic conductivity of LiMnPO_4/C by facilitating the lithium ion diffusion rate in the interior of the materials.

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

Science.gov (United States)

Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

2016-03-21

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

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

Science.gov (United States)

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

2009-03-02

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

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.

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

Science.gov (United States)

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

2012-03-05

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

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

OpenAIRE

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

1994-01-01

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

Nanocrystalline spinel ferrite (MFe2O4, M = Ni, Co, Mn, Mg, Zn) powders prepared by a simple aloe vera plant-extracted solution hydrothermal route

International Nuclear Information System (INIS)

Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan; Amornkitbamrung, Vittaya; Maensiri, Santi

2013-01-01

Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe 2 O 4 (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe 2 O 4 , MgFe 2 O 4 and MnFe 2 O 4 respectively, whereas the samples of NiFe 2 O 4 and ZnFe 2 O 4 show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe 2 O 4 powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates and aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M s of 68.9 emu/g at 10 kOe were observed for the samples of MnFe 2 O 4 . - Abstract: Nanocrystalline spinel ferrite MFe 2 O 4 (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac) 3 , M(acac) 3 (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe 2 O 4 and CoFe 2 O 4 samples contain nanoparticles, whereas the MnFe 2 O 4 and MgFe 2 O 4 samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe 2 O 4 sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe 2 O 4 , MnFe 2 O 4 and MgFe 2 O 4 samples, whereas the samples of NiFe 2 O 4 and ZnFe 2 O 4 exhibit a superparamagnetic behavior

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

NARCIS (Netherlands)

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

1993-01-01

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

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

Science.gov (United States)

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

2015-10-01

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

Exotic Spartina alterniflora invasion alters ecosystem-atmosphere exchange of CH4 and N2O and carbon sequestration in a coastal salt marsh in China.

Science.gov (United States)

Yuan, Junji; Ding, Weixin; Liu, Deyan; Kang, Hojeong; Freeman, Chris; Xiang, Jian; Lin, Yongxin

2015-04-01

Coastal salt marshes are sensitive to global climate change and may play an important role in mitigating global warming. To evaluate the impacts of Spartina alterniflora invasion on global warming potential (GWP) in Chinese coastal areas, we measured CH4 and N2O fluxes and soil organic carbon sequestration rates along a transect of coastal wetlands in Jiangsu province, China, including open water; bare tidal flat; and invasive S. alterniflora, native Suaeda salsa, and Phragmites australis marshes. Annual CH4 emissions were estimated as 2.81, 4.16, 4.88, 10.79, and 16.98 kg CH4 ha(-1) for open water, bare tidal flat, and P. australis, S. salsa, and S. alterniflora marshes, respectively, indicating that S. alterniflora invasion increased CH4 emissions by 57-505%. In contrast, negative N2O fluxes were found to be significantly and negatively correlated (P carbon sequestration rate of S. alterniflora marsh amounted to 3.16 Mg C ha(-1) yr(-1) in the top 100 cm soil profile, a value that was 2.63- to 8.78-fold higher than in native plant marshes. The estimated GWP was 1.78, -0.60, -4.09, and -1.14 Mg CO2 eq ha(-1) yr(-1) in open water, bare tidal flat, P. australis marsh and S. salsa marsh, respectively, but dropped to -11.30 Mg CO2 eq ha(-1) yr(-1) in S. alterniflora marsh. Our results indicate that although S. alterniflora invasion stimulates CH4 emissions, it can efficiently mitigate increases in atmospheric CO2 and N2O along the coast of China. © 2014 John Wiley & Sons Ltd.

Structural relaxation and colour in the spinel-magnesiochromite (MgAl2O4-MgCr2O4) and gahnite-zincochromite (ZnAl2O4-ZnCr2O4) solid solution series

Science.gov (United States)

Hålenius, U.; Andreozzi, G. B.; Skogby, H.

2009-04-01

.5 %, respectively, is determined. Based on a Cr-O bond distance for the CrO6 polyhedron in magnesiochromite and zincochromite of 1.995 and 1.991 Å respectively (O'Neill and Dollase, 1994) and applying the ligand field relationship 10Dq?C×R-5 (R equals the M-O distance of the MO6-polyhedron), Cr-O bond distances in gahnite and spinel with Cr-contents at trace levels are determined to 1.959 and 1.969 Å, respectively. These M-O bond distances are considerably longer than the M-O distances determined for end member gahnite and spinel by XRD-methods (1.9137 and 1.9280 Å, respectively; O'Neill and Dollase, 1994) and shows that there is considerable structural relaxation of M-O bonds in the two present spinel series. The relaxation parameter, ɛ, determined from the optical absorption spectra is 0.59 and 0.63 for the ZnAl2-2xCr2xO4 and MgAl2-2xCr2xO4 and series, respectively. These values are lower than those suggested from X-ray absorption spectroscopy (Juhin et al. 2007), which may be explained by second nearest neighbour interactions. In contrast to what may be expected, the interelectronic repulsion parameter, B, for V ICr3+ decreases with increasing Cr-content and apparent Cr-O bond length in both of the present spinel series . This indicates that interactions between Cr-atoms in neighbouring octahedra become important at increasing Cr-content and result in more covalent Cr-O bonds. This in turn suppresses the energy of 4A2g -4T2g (4F) transition (and calculated 10Dq-values) in octahedrally coordinated Cr3+. Consequently, the values of structural relaxation parameters determined from the optical absorption spectra must be regarded as minimum numbers. Literature Juhin, A., Calas, G., Cabaret, D. and Galoisy, L. (2007): Structural relaxation around Cr3+ in MgAl2O4. Physical Review, B76, 054105. O'Neill, H.St.C. and Dollase, W.A. (1994): Crystal structures and cation distributions in simple spinels from powder XRD structure refinements: MgCr2O4, ZnCr2O4, Fe3O4 and the temperature

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

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

Science.gov (United States)

Zhou, Yong; Zhang, Dong H

2014-11-21

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

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.

Air-sea fluxes of CO2 and CH4 from the Penlee Point Atmospheric Observatory on the south-west coast of the UK

Science.gov (United States)

Yang, Mingxi; Bell, Thomas G.; Hopkins, Frances E.; Kitidis, Vassilis; Cazenave, Pierre W.; Nightingale, Philip D.; Yelland, Margaret J.; Pascal, Robin W.; Prytherch, John; Brooks, Ian M.; Smyth, Timothy J.

2016-05-01

We present air-sea fluxes of carbon dioxide (CO2), methane (CH4), momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO) on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector) were made at three different sampling heights (approximately 15, 18, and 27 m above mean sea level, a.m.s.l.), each from a different period during 2014-2015. At sampling heights ≥ 18 m a.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable ( ≤ ±20 % in the mean) agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air-sea exchange measurements in shelf regions. Covariance air-sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20 ± 3; 38 ± 3; 29 ± 6 µmole m-2 d-1 at 15, 18, 27 m a.m.s.l.) than during falling tides (14 ± 2; 22 ± 2; 21 ± 5 µmole m-2 d-1), consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater). Finally, we found the detection limit of the air-sea CH4 flux by eddy covariance to be 20 µmole m-2 d-1 over hourly timescales (4 µmole m-2 d-1 over 24 h).

CH3Br adsorption on MgO/Mo ultrathin films: A DFT study

Science.gov (United States)

Cipriano, Luis A.; Tosoni, Sergio; Pacchioni, Gianfranco

2018-06-01

The adsorption of methyl bromide on MgO ultrathin films supported on Mo(100) was studied by means of density functional theory calculations, in comparison to the MgO(100) and Mo(100) surfaces. The adsorption energy and geometry were shown to depend on the thickness of the supported oxide film. MgO films as thick as 2ML (or more) display adsorptive properties similar to MgO(100), i.e. the adsorption of CH3Br is mostly due to dispersion and the molecule lies in a tilted geometry almost parallel to the surface. The CH3Br HOMO-LUMO gap is almost unaltered with respect to the gas phase. On metallic Mo(100) surfaces the bonding is completely different with the CH3Br molecule strongly bound and the C-Br bond axis almost vertical with respect to the metal surface. The MgO monolayer supported on Mo exhibits somehow intermediate properties: the tilt angle is larger and the bonding is stronger than on MgO(100), due to the effect of the supporting metal. In this case, a small reduction of the HOMO-LUMO gap of the adsorbed molecule is reported. The results help to rationalize the observed behavior in photodissociation of CH3Br supported on different substrates.

Carbon dynamics and CO2 and CH4 outgassing in the Mekong delta

Science.gov (United States)

Borges, Alberto V.; Abril, Gwenaël; Bouillon, Steven

2018-02-01

We report a data set of biogeochemical variables related to carbon cycling obtained in the three branches (Mỹ Tho, Hàm Luông, Cố Chiên) of the Mekong delta (Bến Tre province, Vietnam) in December 2003, April 2004, and October 2004. Both the inner estuary (upstream of the mouth) and the outer estuary (river plume) were sampled, as well as side channels. The values of the partial pressure of CO2 (pCO2) ranged between 232 and 4085 ppm, O2 saturation level (%O2) between 63 and 114 %, and CH4 between 2 and 2217 nmol L-1, within the ranges of values previously reported in temperate and tropical meso- and macro-tidal estuaries. Strong seasonal variations were observed. In the upper oligohaline estuary, low pCO2 (479-753 ppm) and high %O2 (98-106 %) values were observed in April 2004 most probably related to freshwater phytoplankton growth owing to low freshwater discharge (1400 m3 s-1) and increase in water residence time; during the two other sampling periods with a higher freshwater discharge (9300-17 900 m3 s-1), higher pCO2 (1895-2664 ppm) and lower %O2 (69-84 %) values were observed in the oligohaline part of the estuary. In October 2004, important phytoplankton growth occurred in the offshore part of the river plume as attested by changes in the contribution of particulate organic carbon (POC) to total suspended matter (TSM) (%POC) and the stable isotope composition of POC (δ13C-POC), possibly related to low TSM values (improvement of light conditions for phytoplankton development), leading to low pCO2 (232 ppm) and high %O2 (114 %) values. Water in the side channels in the Mekong delta was strongly impacted by inputs from the extensive shrimp farming ponds. The values of pCO2, CH4, %O2, and the stable isotope composition of dissolved inorganic carbon (δ13C-DIC) indicated intense organic matter degradation that was partly mediated by sulfate reduction in sediments, as revealed by the slope of total alkalinity (TA) and DIC covariations. The δ13C

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.

A Modern Automatic Chamber Technique as a Powerful Tool for CH4 and CO2 Flux Monitoring

Science.gov (United States)

Mastepanov, M.; Christensen, T. R.; Lund, M.; Pirk, N.

2014-12-01

A number of similar systems were used for monitoring of CH4 and CO2 exchange by the automatic chamber method in a range of different ecosystems. The measurements were carried out in northern Sweden (mountain birch forest near Abisko, 68°N, 2004-2010), southern Sweden (forest bog near Hässleholm, 56°N, 2007-2014), northeastern Greenland (arctic fen in Zackenberg valley, 74°N, 2005-2014), southwestern Greenland (fen near Nuuk, 64°N, 2007-2014), central Svalbard (arctic fen near Longyearbyen, 78°N, 2011-2014). Those in total 37 seasons of measurements delivered not only a large amount of valuable flux data, including a few novel findings (Mastepanov et al., Nature, 2008; Mastepanov et al., Biogeosciences, 2013), but also valuable experience with implementation of the automatic chamber technique using modern analytical instruments and computer technologies. A range of high resolution CH4 analysers (DLT-100, FMA, FGGA - Los Gatos Research), CO2 analyzers (EGM-4, SBA-4 - PP Systems; Li-820 - Li-Cor Biosciences), as well as Methane Carbon Isotope Analyzer (Los Gatos Research) has shown to be suitable for precise measurements of fluxes, from as low as 0.1 mg CH4 m-1 d-1 (wintertime measurements at Zackenberg, unpublished) to as high as 2.4 g CH4 m-1 d-1 (autumn burst 2007 at Zackenberg, Mastepanov et al., Nature, 2008). Some of these instruments had to be customized to accommodate 24/7 operation in harsh arctic conditions. In this presentation we will explain some of these customizations. High frequency of concentration measurements (1 Hz in most cases) provides a unique opportunity for quality control of flux calculations; on the other hand, this enormous amount of data can be analyzed only using highly automated algorithms. A specialized software package was developed and improved through the years of measurements and data processing. This software automates the data flow from raw concentration data of different instruments and sensors and various status records

Synthesis and Structural Characterisation of [Ir4(CO8(CH3(m4-h3-Ph2PCCPh(m-PPh2] and of the Carbonylation Product [Ir4(CO8{C(OCH3}(m4-h3-Ph2PCCPh(m-PPh2]; First Evidence for the Formation of a CO Cluster Adduct before CO Insertion

Directory of Open Access Journals (Sweden)

Braga Dario

1999-01-01

Full Text Available Deprotonation of [(mu-HIr4(CO10(mu-PPh2], 1, gives [Ir4(CO10(mu-PPh2]- that reacts with Ph2PCCPh and CH3I to afford [Ir4(CO8(CH3(mu4-eta³-Ph2PCCPh(mu-PPh2], 2 (34%, besides [Ir4(CO9(mu3-eta³-Ph2PC(HCPh(mu-PPh2] and [(mu-HIr4(CO9(Ph2PCºCPh(mu-PPh2]. Compound 2 was characterised by a single crystal X-ray diffraction analysis and exhibits a flat butterfly of metal atoms, with the Ph2PCCPh ligand interacting with all four Ir atoms and the methyl group bonded terminally to a wingtip Ir atom. Carbonylation of 2 yields initially (25 °C, 20 min a CO addition product that, according to VT 31P{¹H} and 13C{¹H} studies, exists in solution in the form of two isomers 4A and 4B (8:1, and then (40 °C, 7 h, the CO insertion product [Ir4(CO8{C(OCH3}(mu4-eta³-Ph2PCCPh(mu-PPh2], 5. The molecular structure of 5, established by an X-ray analysis, is similar to that of 2, except for the acyl group that remains bound to the same Ir atom. The process is reversible at both stages. Treatment of 2 with PPh3 and P(OMe3 affords the CO substitution products [Ir4(CO7L(CH3(mu4-eta³-Ph2PCCPh(mu-PPh2] (L = PPh3, 6 and P(OMe3, 7, instead of the expected CO inserted products. According to the ¹H and 31P{¹H} NMR studies, the PPh3 derivative 6 exists in the form of two isomers (1:1 that differ with respect to the position of this ligand.

Microbial CH4 and N2O consumption in acidic wetlands

Directory of Open Access Journals (Sweden)

Steffen eKolb

2012-03-01

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

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.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

Effect of metal ion and ball milling on the electrochemical properties of M0.5TiOPO4 (M = Ni, Cu, Mg)

International Nuclear Information System (INIS)

Godbole, Vikram A.; Villevieille, Claire; Novák, Petr

2013-01-01

Various metal titanium oxyphosphates, M 0.5 TiOPO 4 (M = Ni, Cu, Mg) were synthesized via modified solution route synthesis. The as synthesized M 0.5 TiOPO 4 (M = Ni, Cu, Mg) were electrochemically tested using galvanostatic cycling, cyclic voltammetry, and rate performance measurements in order to investigate the effect of metal ion (M) on the electrochemical performance of this family of materials. All the studied materials reacted with 3 Li + during the 1st lithiation showing reaction plateaus at different potentials versus Lithium. Similar studies were performed on M 0.5 TiOPO 4 (M = Ni, Cu, Mg) samples with smaller particle size, obtained via ball milling, in order to understand the effect of particle size on the electrochemistry of the materials. The ball milled samples delivered higher specific charge during the 1st cycle showing reaction plateaus at different potentials, poorer capacity retention, and poorer rate capability as compared to the as synthesized ones. This was attributed to a change in morphology and particle size of the samples upon ball milling. Amongst all the tested materials, the as synthesized Cu 0.5 TiOPO 4 showed the best electrochemistry. The ball milled Mg 0.5 TiOPO 4 reacted with ∼5.5 Li + during 1st lithiation (as compared to 3 Li + expected from this family of compounds) and 3.3 Li + during the 1st delithiation (rather than the expected 2 Li + ). This suggests a reaction mechanism where Mg 0.5 TiOPO 4 undergoes a phase transformation forming Mg 0 , which reversibly alloys with 2.5 extra Li + . Thus the electrochemical cycling of Mg 0.5 TiOPO 4 gives insights into the reaction mechanism in this family of materials

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

Directory of Open Access Journals (Sweden)

Knut Arne Birkedal

2015-05-01

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

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

Science.gov (United States)

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

2017-12-01

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

New metal-organic polygons involving MM quadruple bonds: M8(O2CtBu)4(mu-SC4H2-3,4-{CO2}2)6 (M=Mo, W).

Science.gov (United States)

Byrnes, Matthew J; Chisholm, Malcolm H; Patmore, Nathan J

2005-12-12

The reactions between M2(O2CtBu)4, where M=Mo or W, and thienyl-3,4-dicarboxylic acid (0.5-1.5 equiv) in toluene proceed via a series of detectable intermediates to the compounds M8(O2CtBu)4(mu-SC4H2-3,4-{CO2}2)6, which are isolated as air-sensitive yellow (M=Mo) or red (M=W) powders and show parent molecular ions in their mass spectra (MALDI). The structure of the molybdenum complex was determined by single-crystal X-ray crystallography and shown to contain an unusual M8 polygon involving four Mo2 quadruply bonded units linked via the agency of the six 3,4-thienylcarboxylate groups. The structure has crystallographically imposed S4 symmetry and may be described in terms of a highly distorted tetrahedron of Mo2 units or a bisphenoid in which two Mo2 units are linked by a thienyldicarboxylate such that intramolecular Mo2...O bonding is present, while the other thienylcarboxylate bridges merely serve to link these two [Mo2]...[Mo2] units together. The color of the compounds arises from intense M2 delta-to-thienyl pi transitions and, in THF, the complexes are redox-active and show four successive quasi-reversible oxidation waves. The [M8]+ radical cations, generated by one-electron oxidation with AgPF6, are shown to be valence-trapped (class II) by UV-vis-near-IR and electron paramagnetic resonance spectroscopy. These results are supported by the electronic structure calculations on model compounds M8(O2CH)4(mu-SC4H2-3,4-{CO}2)6 employing density functional theory that reveal only a small splitting of the M2 delta manifold via mixing with the 3,4-thienylcarboxylate pi system.

Sr{sub 2}CoMoO{sub 6} anode for solid oxide fuel cell running on H{sub 2} and CH{sub 4} fuels

Energy Technology Data Exchange (ETDEWEB)

Zhang, Ping [Engineering Research Center of Nano-GEO Materials of Education Ministry, China University of Geosciences, Wuhan 430074 (China); Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Huang, Yun-Hui [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074 (China); Cheng, Jin-Guang; Goodenough, John B. [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Mao, Zong-Qiang [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

2011-02-15

The double perovskite Sr{sub 2}CoMoO{sub 6-{delta}} was investigated as a candidate anode for a solid oxide fuel cell (SOFC). Thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD) showed that the cation array is retained to 800 C in H{sub 2} atmosphere with the introduction of a limited concentration of oxide-ion vacancies. Stoichiometric Sr{sub 2}CoMoO{sub 6} has an antiferromagnetic Neel temperature T{sub N} {approx} 37 K, but after reduction in H{sub 2} at 800 C for 10 h, long-range magnetic order appears to set in above 300 K. In H{sub 2}, the electronic conductivity increases sharply with temperature in the interval 400 C < T < 500 C due to the onset of a loss of oxygen to make Sr{sub 2}CoMoO{sub 6-{delta}} a good mixed oxide-ion/electronic conductor (MIEC). With a 300-{mu}m-thick La{sub 0.8}Sr{sub 0.12}Ga{sub 0.83}Mg{sub 0.17}O{sub 2.815} (LSGM) as oxide-ion electrolyte and SrCo{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} as the cathode, the Sr{sub 2}CoMoO{sub 6-{delta}} anode gave a maximum power density of 1017 mW cm{sup -2} in H{sub 2} and 634 mW cm{sup -2} in wet CH{sub 4}. A degradation of power in CH{sub 4} was observed, which could be attributed to coke build up observed by energy dispersive spectroscopy (EDS). (author)

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

Science.gov (United States)

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

2015-01-01

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

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

Science.gov (United States)

Gesi, Kazuo

2002-05-01

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

SYNGAS PRODUCTION FROM CO2-REFORMING OF CH4 OVER SOL-GEL SYNTHESIZED Ni-Co/Al2O3-MgO-ZrO2 NANOCATALYST: EFFECT OF ZrO2 PRECURSOR ON CATALYST PROPERTIES AND PERFORMANCE

Directory of Open Access Journals (Sweden)

Seyed Mehdi Sajjadi

2015-05-01

Full Text Available Ni-Co/Al2O3-MgO-ZrO2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH and zirconyl nitrate solution (ZNS, was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO2-reforming of CH4. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS. FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH4 and CO2 conversions were 97.2 and 99% at 850 ºC, respectively. Furthermore, NCAMZ-ZNS demonstrated a stable yield with H2/CO close to unit value during the 1440 min stability test.

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

Science.gov (United States)

Minoda, Tomomi; Kimura, Mamoto; Wada, Eitaro

1996-09-01

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

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.

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.

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...

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.

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

Science.gov (United States)

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

2016-05-01

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

1- 4 Falodun

African Journals Online (AJOL)

DR. AMIN

45.3. 2.31 (dd, J = 7.5, 12.8). CH2. 9. 70.7. 5.62 m. CH. 10. 122.9. 5.09 m. CH. 11. 131.2. -. C. 12. 25.5. 1.71 s. CH3. 13. 27.8. 1.30 s. CH3. 14. 16.8. 1.59 s. CH3. 15. 18.2. 1.70 s. CH3. CH3CO. 171.4. -. CH3. CH3CO. 20.2. 1.89 s. CH3. Organisms. Concentrations of seed extracts (mg/ml). 2.5. 5. 10. 20. 25. 50. 100. 200. E.coli.

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin, West-Central Alabama

Science.gov (United States)

Gruszkiewicz, M.S.; Naney, M.T.; Blencoe, J.G.; Cole, D.R.; Pashin, J.C.; Carroll, R.E.

2009-01-01

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO2, CH4, approximately equimolar CO2 + CH4 mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45-150????m, 1-2??mm, and 5-10??mm) of crushed coal were performed at 40????C and 35????C over a pressure range of 1.4-6.9??MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO2 adsorption on both dry and water-saturated coal is much more rapid than CH4 adsorption; (2) water saturation decreases the rates of CO2 and CH4 adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO2 or CH4 adsorption if the coal is not previously exposed to CO2; (3) retention of adsorbed CO2 on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45-150????m size fraction compared to the two coarser fractions. ?? 2008 Elsevier B.V.

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

Thermal conductivity of M-Si-N (M = Mg, Ca, Sr, Ba) compounds with varying M/Si ratio

NARCIS (Netherlands)

Hintzen, H.T.J.M.; Bruls, R.J.; Delsing, A.C.A.; Itatani, K.; Tanaka, S.; With, de G.; Metselaar, R.

2002-01-01

The thermal cond. of M-Si-N (M = Mg, Ca, Sr, Ba) compds. was examd. The emphasis is on MgSiN2 (a material which can be derived from AlN by replacing systematically 2Al3+ by Mg2+/Si4+), and Si3N4 (the well known b-modification as well as the recently discovered cubic modification with the spinel

A theoretical study of the hydrogen-storage potential of (H2)4CH4 in metal organic framework materials and carbon nanotubes.

Science.gov (United States)

Li, Q; Thonhauser, T

2012-10-24

The hydrogen-methane compound (H(2))(4)CH(4)-or for short H4M-is one of the most promising hydrogen-storage materials. This van der Waals compound is extremely rich in molecular hydrogen: 33.3 mass%, not including the hydrogen bound in CH(4); including it, we reach even 50.2 mass%. Unfortunately, H4M is not stable under ambient pressure and temperature, requiring either low temperature or high pressure. In this paper, we investigate the properties and structure of the molecular and crystalline forms of H4M, using ab initio methods based on van der Waals DFT (vdW-DF). We further investigate the possibility of creating the pressures required to stabilize H4M through external agents such as metal organic framework (MOF) materials and carbon nanotubes, with very encouraging results. In particular, we find that certain MOFs can create considerable pressure for H4M in their cavities, but not enough to stabilize it at room temperature, and moderate cooling is still necessary. On the other hand, we find that all the investigated carbon nanotubes can create the high pressures required for H4M to be stable at room temperature, with direct implications for new and exciting hydrogen-storage applications.

The Influence of Climate Change on CO2 and CH4 Concentration Near Closed Shaft - Numerical Simulations

Science.gov (United States)

Wrona, Paweł

2017-09-01

Given the scientific consensus pointing to climate change, the more extreme weather events associated with this will lead to deeper pressure drops. As has already been stated, pressure drops are the main cause of gas flow from underground sites to the surface. This article presents the results of numerical simulations of the change in distribution of CO2 and CH4 near a closed mining shaft under the predicted baric tendency. Simulations have been undertaken by means of the FDS software package with the Pyrosim graphical interface - a CFD tool for fire and ventilation analysis. Assumptions have been based on previous results of in-situ measurements. The results (determined for a height of 1m above the ground) were compared to the following levels (later in the text comparison levels): for CO2 0.1%vol. according to Pettenkoffer's scale and 2.5%vol. for CH4 as the half of Lower Explosive Limit (LEL). The results show that the deeper baric drops anticipated could lead to a wider spread of both greenhouse gases in the vicinity of the shaft, especially along the prevailing wind direction. According to the results obtained, CO2 and CH4 with concentrations above their comparison levels are expected at a distance greater than 50m from the shaft when wind is present for CO2 and at a distance of 4.5m for CH4. Subsequent analysis of the results enabled the determination of functions for describing the concentration of gases along the wind direction line under the projected pressure drop. The results relate to a particular case, although the model could easily be modified to any other example of gas emissions from underground sites.

Nanocrystalline spinel ferrite (MFe{sub 2}O{sub 4}, M = Ni, Co, Mn, Mg, Zn) powders prepared by a simple aloe vera plant-extracted solution hydrothermal route

Energy Technology Data Exchange (ETDEWEB)

Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan; Amornkitbamrung, Vittaya [Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Integrated Nanotechnology Research Center (INRC), Khon Kaen University, Khon Kaen 40002 (Thailand); Maensiri, Santi, E-mail: santimaensiri@gmail.com [School of Physics, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand)

2013-06-01

Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4} and MnFe{sub 2}O{sub 4} respectively, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe{sub 2}O{sub 4} powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates and aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M{sub s} of 68.9 emu/g at 10 kOe were observed for the samples of MnFe{sub 2}O{sub 4}. - Abstract: Nanocrystalline spinel ferrite MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac){sub 3}, M(acac){sub 3} (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} samples contain nanoparticles, whereas the MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe{sub 2}O{sub 4} sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe{sub 2}O{sub 4}, MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples, whereas the

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

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

International Nuclear Information System (INIS)

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

1990-01-01

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

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...

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

Directory of Open Access Journals (Sweden)

Yu JIANG

2013-11-01

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

Mechanical Properties and Fabrication of Nanostructured Mg_2SiO_4-MgAl_2O_4 Composites by High-Frequency Induction Heated Combustion

International Nuclear Information System (INIS)

Shon, In-Jin; Kang, Hyun-Su; Hong, Kyung-Tae; Doh, Jung-Mann; Yoon, Jin-Kook

2011-01-01

Nanopowders of MgO, Al_2O_3 and SiO_2 were made by high energy ball milling. The rapid sintering of nanostructured MgAl_2O_4-Mg_2SiO_4 composites was investigated by a high-frequency induction heating sintering process. The advantage of this process is that it allows very quick densification to near theoretical density and inhibition of grain growth. Nanocrystalline materials have received much attention as advanced engineering materials with improved physical and mechanical properties. As nanomaterials possess high strength, high hardness, excellent ductility and toughness, undoubtedly, more attention has been paid for the application of nanomaterials. Highly dense nanostructured MgAl_2O_4-Mg_2SiO_4 composites were produced with simultaneous application of 80 MPa pressure and induced output current of total power capacity (15 kW) within 2 min. The sintering behavior, gain size and mechanical properties of MgAl_2O_4-Mg_2SiO_4 composites were investigated.

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.

Mg-containing hydroxyapatite coatings on Ti-6Al-4V alloy for dental materials

Science.gov (United States)

Yu, Ji-Min; Choe, Han-Cheol

2018-02-01

In this study, Mg-containing hydroxyapatite coatings on Ti-6A1-4 V alloy for dental materials were researched using various experimental instruments. Plasma electrolytic oxidation (PEO) was performed in electrolytes containing Mg (symbols of specimens: CaP, 5M%, 10M%, and 20M%) at 280 V for 3 min. The electrolyte used for PEO was produced by mixing Ca(CH3COO)2·H2O, C3H7NaCaO6P, and MgCl2·6H2O. The phases and composition of the oxide films were evaluated by X-ray diffraction and field-emission scanning electron microscopy with energy dispersive X-ray spectrometry. The irregularity of the surface, pore size, and number of pores decreased as the Mg concentration increased. The ratio of the areas occupied and not occupied by pores decreased as the Mg concentration increased, with the numbers of both large and small pores decreasing with increasing Mg concentration. The number of particles on the internal surfaces of pores was increased as the Mg content increased. Mg content of all samples containing Mg ions showed higher in the pore outside than that of pore inside, whereas the Ca content was higher inside the pores. The P content of samples with the addition of Mg ions showed higher values inside the pores than outside. The Ca/P and [Mg + Ca]/P molar ratios in the PEO films decreased with Mg content. The crystallite size of anatase was increased with increasing Mg concentration in the solution.

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.

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.

Thermodynamic investigation of the ternary mixed aqueous electrolyte (MgCl{sub 2} + MgSO{sub 4}) system by potentiometric method at T = 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Bagherinia, Mohammad A., E-mail: mabagherinia@yahoo.com [Department of Chemistry, Faculty of Science, Lahijan Branch, Islamic Azad University, Lahijan (Iran, Islamic Republic of); Giahi, Masoud; Pournaghdy, Mohammad; Vaghar, Gholam R. [Department of Chemistry, Faculty of Science, Lahijan Branch, Islamic Azad University, Lahijan (Iran, Islamic Republic of)

2012-01-15

Highlights: > In this study we investigated the thermodynamic properties of MgCl{sub 2} + MgSO{sub 4} + H{sub 2}O. > The method used in this work was potentiometric method. > Mg-ISE and the Ag/AgCl electrodes used in this work had a good Nernst response. > The experimental results obeyed the Harned rule. > The Pitzer model could be used to describe this ternary system satisfactorily. - Abstract: This work reports the results of thermodynamic investigation of the ternary mixed-electrolyte system (MgCl{sub 2} + MgSO{sub 4} + H{sub 2}O). The investigation was performed based on Pitzer ion interaction model by using the potentiometric technique at T = 298.15 K. The mean activity coefficients of MgCl{sub 2} in the mixed aqueous electrolyte system were determined on the galvanic cell without liquid junction of the type: Mg-ISE|MgCl{sub 2} (m{sub A}), MgSO{sub 4} (m{sub B}), H{sub 2}O|Ag/AgCl over total ionic strengths from (0.001 to 8.000) mol . kg{sup -1} for different series of salt ratio r (r=m{sub MgCl{sub 2}}/m{sub MgSO{sub 4}}=2.5,5.0,7.5,10.0,15.0 and pure MgCl{sub 2}). The PVC based magnesium ion-selective electrode (Mg-ISE) and the Ag/AgCl electrode used in this work were made in our laboratory and had a reasonably good Nernst response. The experimental results obeyed the Harned rule, and the Pitzer model could be used to describe this ternary system satisfactorily. Pitzer ion-interaction parameters for mixed salts were determined for this system. Then, these parameters ({theta}{sub ClSO{sub 4}}=0.0252{+-}0.0042, {psi}{sub MgClSO{sub 4}}=-0.0049{+-}0.0003) were used to calculate the values of the mean activity coefficients of MgSO{sub 4}, the osmotic coefficients of water ({phi}) and the excess Gibbs free energies of solution (G{sup E}) for the whole series of the studied electrolyte systems.

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

Science.gov (United States)

Zheng, J.

2016-12-01

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

MgO-hybridized TiO{sub 2} interfacial layers assisting efficiency enhancement of solid-state dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Sakai, Nobuya; Ikegami, Masashi; Miyasaka, Tsutomu, E-mail: miyasaka@toin.ac.jp [Graduate School of Engineering, Toin University of Yokohama, 1614 Kurogane-cho, Aoba, Yokohama, Kanagawa 225-8502 (Japan)

2014-02-10

Interfacial modification of a thin TiO{sub 2} compact layer (T-CL) by hybridization with MgO enhanced the quantum conversion efficiency of solid-state dye-sensitized solar cells (ssDSSCs) comprising a multilayer structure of transparent electrode/T-CL/dye-sensitized mesoporous TiO{sub 2}/hole conductor/metal counter electrode. The Mg(CH{sub 3}COO){sub 2} treatment was employed to introduce a MgO-TiO{sub 2} CL (T/M-CL), which enhanced the physical connection and conduction between the CL and mesoporous semiconductor layer as a consecutive interface, owing to the dehydration reaction of Mg(CH{sub 3}COO){sub 2}. The photocurrent density of ssDSSC was increased 33% by the T/M-CL compared with the T-CL, using an equivalent amount of adsorbed dye. The ssDSSC with the T/M-CL yielded the highest efficiency of 4.02% under irradiation at 100 mW cm{sup −2}. The electrical impedance spectroscopy showed that the charge-transfer resistance (R{sub ct}) of the photoelectrode with T/M-CL was reduced by 300 Ω from the reference non-treated T-CL electrode. Characterized by the intrinsically low R{sub ct} of the compact layer, the T/M-CL is capable of improving the photovoltaic performance of solid-state sensitized mesoscopic solar cells.

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

Science.gov (United States)

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

2017-04-01

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

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

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

Science.gov (United States)

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

2016-09-26

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

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

Science.gov (United States)

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

2016-09-01

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

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

Synthesized of PEG-6000 coated MgFe2O4 nanoparticles based on natural iron sand by co-precipitation method

Science.gov (United States)

Setiadi, E. A.; Simbolon, S.; Saputra, A. S. P.; Marlianto, E.; Djuhana; Kurniawan, C.; Yunus, M.; Sebayang, P.

2018-02-01

The polymer coated Magnesium Ferrite nanoparticles (MgFe2O4) based on natural iron sand, Mg(CH3COO)2.4H2O, and PEG-6000 have been successfully prepared by co-precipitation method. The mass variation of PEG-6000 content was from 0 to 12 gram. It was prepared at synthesize temperature of 70°C. The PEG coating reduced the effect of agglomeration, so the coercivity value can be closed to soft magnets. The nanoparticle of synthesized has MgFe2O4 single phase and cubic spinel structure. The bonding of MgFe2O4 and PEG-6000 as a coating material was confirmed by FTIR curve. The MgFe2O4 density decreased with the increasing of PEG 6000 content. On the other hand, the coercivity value was slightly reduced as the addition of PEG-6000, with the lowest value was obtained on 8 gram PEG content. The optimum condition is obtained at addition of 8 gram PEG 6000 to MgFe2O4, with coercivity, saturation, and remanence are 198.41 Oe, 52.53 emu/g, and 8.51 emu/g, respectively. So that, the sample is widely used as absorbance material of heavy metal.

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

Science.gov (United States)

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

2016-07-01

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

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

Directory of Open Access Journals (Sweden)

H. Schaefer

2012-09-01

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

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

Science.gov (United States)

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

2015-01-01

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

Synthesis and performance of Li{sub 3}(V{sub 1-x}Mg{sub x}){sub 2}(PO{sub 4}){sub 3} cathode materials

Energy Technology Data Exchange (ETDEWEB)

Dai, Changsong; Chen, Zhenyu; Jin, Haizu; Hu, Xinguo [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

2010-09-01

In order to search for cathode materials with better performance, Li{sub 3}(V{sub 1-x}Mg{sub x}){sub 2}(PO{sub 4}){sub 3} (0, 0.04, 0.07, 0.10 and 0.13) is prepared via a carbothermal reduction (CTR) process with LiOH.H{sub 2}O, V{sub 2}O{sub 5}, Mg(CH{sub 3}COO){sub 2}.4H{sub 2}O, NH{sub 4}H{sub 2}PO{sub 4}, and sucrose as raw materials and investigated by X-ray diffraction (XRD), scanning electron microscopic (SEM) and electrochemical impedance spectrum (EIS). XRD shows that Li{sub 3}(V{sub 1-x}Mg{sub x}){sub 2}(PO{sub 4}){sub 3} (x = 0.04, 0.07, 0.10 and 0.13) has the same monoclinic structure as undoped Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} while the particle size of Li{sub 3}(V{sub 1-x}Mg{sub x}){sub 2}(PO{sub 4}){sub 3} is smaller than that of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} according to SEM images. EIS reveals that the charge transfer resistance of as-prepared materials is reduced and its reversibility is enhanced proved by the cyclic votammograms. The Mg{sup 2+}-doped Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} has a better high rate discharge performance. At a discharge rate of 20 C, the discharge capacity of Li{sub 3}(V{sub 0.9}Mg{sub 0.1}){sub 2}(PO{sub 4}){sub 3} is 107 mAh g{sup -1} and the capacity retention is 98% after 80 cycles. Li{sub 3}(V{sub 0.9}Mg{sub 0.1}){sub 2}(PO{sub 4}){sub 3}//graphite full cells (085580-type) have good discharge performance and the modified cathode material has very good compatibility with graphite. (author)

Regional scale variations of atmospheric CO2 and CH4 from satellite observation

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Directory of Open Access Journals (Sweden)

Amanda eLawter

2015-07-01

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

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.

SOIL 222Rn CONCENTRATION, CO2 AND CH4 FLUX MEASUREMENTS AROUND THE JWALAMUKHI AREA OF NORTH-WEST HIMALAYAS, INDIA.

Science.gov (United States)

Kumar, Arvind; Walia, Vivek; Yang, Tsanyao Frank; Fu, Ching-Chou; Singh, Surinder; Bajwa, Bikramjit Singh; Arora, Vishal

2016-10-01

Soil 222 Rn concentration, CO 2 and CH 4 flux measurements were conducted around the Jwalamukhi area of North-West Himalayas, India. During this study, around 37 soil gas points and flux measurements were taken with the aim to assure the suitability of this method in the study of fault zones. For this purpose, RAD 7 (Durridge, USA) was used to monitor radon concentrations, whereas portable diffuse flux meter (West Systems, Italy) was used for the CO 2 and CH 4 flux measurements. The recorded radon concentration varies from 6.1 to 34.5 kBq m -3 with an average value of 16.5 kBq m -3 The anomalous value of radon concentrations was recorded between Jwalamukhi thrust and Barsar thrust. The recorded average of CO 2 and CH 4 flux were 11.8 and 2.7 g m -2 day -1 , respectively. The good correlation between anomalous CO 2 flux and radon concentrations has been observed along the fault zone in the study area, suggesting that radon migration is dependent on CO 2 . © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Seasonal changes of CO2, CH4 and N2O fluxes in relation to land-use change in tropical peatlands located in coastal area of South Kalimantan

International Nuclear Information System (INIS)

Inubushi, K.; Furukawa, Y.; Hadi, A.; Purnomo, E.; Tsuruta, H.

2003-01-01

Tropical peatland could be a source of greenhouse gases emission because it contains large amounts of soil carbon and nitrogen. However these emissions are strongly influenced by soil moisture conditions. Tropical climate is characterized typically by wet and dry seasons. Seasonal changes in the emission of carbon dioxide (CO 2 ), methane (CH 4 ) and nitrous oxide (N 2 O) were investigated over a year at three sites (secondary forest, paddy field and upland field) in the tropical peatland in South Kalimantan, Indonesia. The amount of these gases emitted from the fields varied widely according to the seasonal pattern of precipitation, especially methane emission rates were positively correlated with precipitation. Converting from secondary forest peatland to paddy field tended to increase annual emissions of CO 2 and CH 4 to the atmosphere (from 1.2 to 1.5 kg CO 2 -C m -2 y -1 and from 1.2 to 1.9 g CH 4 -C m -2 y -1 ), while changing land-use from secondary forest to upland tended to decrease these gases emissions (from 1.2 to 1.0 kg CO 2 -C m -2 y -1 and from 1.2 to 0.6 g CH 4 -C m -2 y -1 ), but no clear trend was observed for N 2 O which kept negative value as annual rates at three sites. (Author)

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

Science.gov (United States)

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

2008-12-01

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

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

source of nitrogen in the water column of the PSR is the NH4+ produced during the mineralisation of the OM at the bottom of the reservoir. In OW, the production of NO3- and N2O is enhanced compared to the FF. As a result, N2O concentrations are three times higher at the bottom of OW but surface concentrations are similar in the FF and OW. CO2 diffusive fluxes are 40% higher and CH4 diffusive fluxes are three times higher in FF (CO2: 42±20 mmol m-2 d-1 ; CH4: 0.7±1.4 mmol m-2 d-1) than in OW (CO2: 27±17 mmol m-2 d-1 ; CH4: 0.2±0.3 mmol m-2 d-1). In shallow FF, average CH4 ebullition is 3±10 mmol m-2 d-1 whereas ebullition was never observed in OW. N2O emissions did not exhibit any spatial variability (9±4 μmol m-2 d-1). At the PSR, FF which represents one third of the surface area, is responsible of half of the GHG emissions from the reservoir. This implies that the emissions from most of the tropical reservoirs flooding primary forest need to be reassessed since FF environments are usually overlooked.

Optimisation of expansion liquefaction processes using mixed refrigerant N_2–CH_4

International Nuclear Information System (INIS)

Ding, He; Sun, Heng; He, Ming

2016-01-01

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

CO2 and CH4 exchange by Phragmites australis under different climates

Science.gov (United States)

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

2015-04-01

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

Phase formation, morphology and magnetic properties of MgFe{sub 2}O{sub 4} nanoparticles synthesized by hydrothermal technique

Energy Technology Data Exchange (ETDEWEB)

Nonkumwong, Jeeranan [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Ananta, Supon [Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Jantaratana, Pongsakorn [Department of Physics, Faculty of Science, Kasetsart University, Bangkok 11900 (Thailand); Phumying, Santi; Maensiri, Santi [Advanced Materials Physics Laboratory (Amp.), School of Physics, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); Srisombat, Laongnuan, E-mail: slaongnuan@yahoo.com [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand)

2015-05-01

In the present work, the processing conditions for obtaining monodispersed magnesium ferrite (MgFe{sub 2}O{sub 4}) nanoparticles with the desired morphology and relatively high saturation magnetization via hydrothermal technique were developed. For the first time, the effects of base type and reaction conditions (i.e. temperature and time) on phase formation, morphology and magnetic properties of the obtained products were determined by using a combination of XRD, TEM/EDX and VSM techniques. It is seen that the saturation magnetization of the particles can be increased by employing lower reaction temperature and/or shorter reaction time, while narrow size distribution of the particles can be maintained. In addition, it was found that pure phase of superparamagnetic MgFe{sub 2}O{sub 4} nanoparticles with the smallest size of about 65 nm was obtained by using CH{sub 3}COONa as a base at 180 °C for 14 h. - Highlights: • Preparation of MgFe{sub 2}O{sub 4} nanoparticles by hydrothermal method. • Effects of base and reaction conditions on formation and morphology MgFe{sub 2}O{sub 4} particles. • Producing the 65 nm MgFe{sub 2}O{sub 4} nanoparticles with superparamagnetic property.

Electric conductivity of solid solutions the Cs3-2xMxPO4 (M=Ba, Sr, Ca, Mg) systems

International Nuclear Information System (INIS)

Burmakin, E.I.; Stroev, S.S.; Shekhtman, G.Sh.; Antonov, B.D.

2003-01-01

The solid solutions in the Cs 3-2x M x PO 4 (M=Ba, Sr, Ca, Mg) system are synthesized and their thermal behavior and electric conductivity are studied. The introduction of the alkaline earth metal cations into cesium orthophosphates is accompanied by the shift of the phase transition occurring in the pure Cs 3 PO 4 at 450-620 Deg C into the low-temperature area as well as by increase in the cesium-cation conductivity at low temperatures. The electric conductivity in the area of existence of the Cs 3 PO 4 high-temperature modification slightly depends on the availability and concentration of the modifying additions, which make it possible to suppose the calcium sublattice structural disordering [ru

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

Directory of Open Access Journals (Sweden)

H. Jamali

2013-04-01

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

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

Science.gov (United States)

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

2013-04-01

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

Air–sea fluxes of CO2 and CH4 from the Penlee Point Atmospheric Observatory on the south-west coast of the UK

Directory of Open Access Journals (Sweden)

M. Yang

2016-05-01

Full Text Available We present air–sea fluxes of carbon dioxide (CO2, methane (CH4, momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector were made at three different sampling heights (approximately 15, 18, and 27 m above mean sea level, a.m.s.l., each from a different period during 2014–2015. At sampling heights  ≥  18 m a.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable ( ≤  ±20 % in the mean agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air–sea exchange measurements in shelf regions. Covariance air–sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20 ± 3; 38 ± 3; 29 ± 6 µmole m−2 d−1 at 15, 18, 27 m a.m.s.l. than during falling tides (14 ± 2; 22 ± 2; 21 ± 5 µmole m−2 d−1, consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater. Finally, we found the detection limit of the air–sea CH4 flux by eddy covariance to be 20 µmole m−2 d−1 over hourly timescales (4 µmole m−2 d−1 over 24 h.

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.

Syngas production from CO{sub 2}-reforming of CH{sub 4} over sol-gel synthesized Ni-Co/Al{sub 2}O{sub 3}-MgOZrO{sub 2} nanocatalyst: effect of ZrO{sub 2} precursor on catalyst properties and performance

Energy Technology Data Exchange (ETDEWEB)

Sajjadi, Seyed Mehdi; Haghighi, Mohammad; Rahmani, Farhad, E-mail: haghighi@sut.ac.ir [Reactor and Catalysis Research Center, Sahand University of Technology, Tabriz (Iran, Islamic Republic of)

2015-05-15

Ni-Co/Al{sub 2}O{sub 3}-MgO-ZrO{sub 2} nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO{sub 2}-reforming of CH{sub 4}. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH{sub 4} and CO{sub 2} conversions were 97.2 and 99% at 850 °C, respectively. Furthermore, NCAMZZNS demonstrated a stable yield with H{sub 2}/CO close to unit value during the 1440 min stability test. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Pure- and Mixed-Gas Permeation Properties of Highly Selective and Plasticization Resistant Hydroxyl-Diamine-Based 6FDA Polyimides for CO2/CH4 Separation

KAUST Repository

Alaslai, Nasser Y.

2016-01-05

The effect of hydroxyl functionalization on the m-phenylene diamine moiety of 6FDA dianhydride-based polyimides was investigated for gas separation applications. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 atm. The introduction of hydroxyl groups in the diamine moiety of 6FDA-diaminophenol (DAP) and 6FDA-diamino resorcinol (DAR) polyimides tightened the overall polymer structure due to increased charge transfer complex formation compared to unfunctionalized 6FDA-m-phenylene diamine (mPDA). The BET surface areas based on nitrogen adsorption of 6FDA-DAP (54 m2g−1) and of 6FDA-DAR (45 m2g−1) were ~18% and 32% lower than that of 6FDA-mPDA (66 m2g−1). 6FDA-mPDA had a pure-gas CO2 permeability of 14 Barrer and CO2/CH4 selectivity of 70. The hydroxyl-functionalized polyimides 6FDA-DAP and 6FDA-DAR exhibited very high pure-gas CO2/CH4 selectivities of 92 and 94 with moderate CO2 permeability of 11 and 8 Barrer, respectively. It was demonstrated that hydroxyl-containing polyimide membranes maintained very high CO2/CH4 selectivity (~ 75 at CO2 partial pressure of 10 atm) due to CO2 plasticization resistance when tested under high-pressure mixed-gas conditions. Functionalization with hydroxyl groups may thus be a promising strategy towards attaining highly selective polyimides for economical membrane-based natural gas sweetening.

Pure- and Mixed-Gas Permeation Properties of Highly Selective and Plasticization Resistant Hydroxyl-Diamine-Based 6FDA Polyimides for CO2/CH4 Separation

KAUST Repository

Alaslai, Nasser Y.; Ghanem, Bader; Alghunaimi, Fahd; Litwiller, Eric; Pinnau, Ingo

2016-01-01

The effect of hydroxyl functionalization on the m-phenylene diamine moiety of 6FDA dianhydride-based polyimides was investigated for gas separation applications. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 atm. The introduction of hydroxyl groups in the diamine moiety of 6FDA-diaminophenol (DAP) and 6FDA-diamino resorcinol (DAR) polyimides tightened the overall polymer structure due to increased charge transfer complex formation compared to unfunctionalized 6FDA-m-phenylene diamine (mPDA). The BET surface areas based on nitrogen adsorption of 6FDA-DAP (54 m2g−1) and of 6FDA-DAR (45 m2g−1) were ~18% and 32% lower than that of 6FDA-mPDA (66 m2g−1). 6FDA-mPDA had a pure-gas CO2 permeability of 14 Barrer and CO2/CH4 selectivity of 70. The hydroxyl-functionalized polyimides 6FDA-DAP and 6FDA-DAR exhibited very high pure-gas CO2/CH4 selectivities of 92 and 94 with moderate CO2 permeability of 11 and 8 Barrer, respectively. It was demonstrated that hydroxyl-containing polyimide membranes maintained very high CO2/CH4 selectivity (~ 75 at CO2 partial pressure of 10 atm) due to CO2 plasticization resistance when tested under high-pressure mixed-gas conditions. Functionalization with hydroxyl groups may thus be a promising strategy towards attaining highly selective polyimides for economical membrane-based natural gas sweetening.

Changes in concentration and (delta) 13C value of dissolved CH4, CO2 and organic carbon in rice paddies under ambient and elevated concentrations of atmospheric CO2

International Nuclear Information System (INIS)

Weiguo Cheng; Yagi, Kazuyuki; Sakai, Hidemitsu; Hua Xu; Kobayashi, Kazuhiko

2005-01-01

Changes in concentration and (delta) 13 C value of dissolved CH 4 , CO 2 and organic carbon (DOC) in floodwater and soil solution from a Japanese rice paddy were studied under ambient and elevated concentrations of atmospheric CO 2 in controlled environment chambers. The concentrations of dissolved CH 4 in floodwater increased with rice growth (with some fluctuation), while the concentrations of CO 2 remained between 2.9 to 4.4 and 4.2 to 5.8 μg C mL -1 under conditions of ambient and elevated CO 2 concentration, respectively. The amount of CH 4 dissolved in soil solution under elevated CO 2 levels was significantly lower than under ambient CO 2 in the tillering stage, implying that the elevated CO 2 treatment accelerated CH 4 oxidation during the early stage of growth. However, during later stages of growth, production of CH 4 increased and the amount of CH 4 dissolved in soil solution under elevated CO 2 levels was, on average, greater than that under ambient CO 2 conditions. Significant correlation existed among the (delta) 13 C values of dissolved CH 4 , CO 2 , and DOC in floodwater (except for the samples taken immediately after pulse feeding with 13 C enriched CO 2 ), indicating that the origins and cycling of CH 4 , CO 2 and DOC were related. There were also significant correlations among the (delta) 13 C values of CH 4 , CO 2 and DOC in the soil solution. The turnover rate of CO 2 in soil solution was most rapid in the panicle formation stage of rice growth and that of CH 4 fastest in the grain filling stage. (Author)

Thermodynamic study of (alkyl esters + {alpha},{omega}-alkyl dihalides) VII. H{sub m}{sup E} and V{sub m}{sup E} for 20 binary mixtures {l_brace}xC{sub u-1}H{sub 2u-1}CO{sub 2}C{sub 3}H{sub 7} + (1 - x){alpha},{omega}-ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl{r_brace}, where u = 1 to 4, {alpha} = 1 and v = {omega} = 2 to 6. An analysis of behavior using the COSMO-RS methodology

Energy Technology Data Exchange (ETDEWEB)

Marrero, E. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos (www.thermo.ulpgc.es), Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain); Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos (www.thermo.ulpgc.es), Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain)], E-mail: jortega@dip.ulpgc.es; Palomar, J. [Seccion de Ingenieria Quimica, Dpto. de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

2009-03-15

Summary: Excess enthalpies H{sub m}{sup E} and excess volumes V{sub m}{sup E} obtained at a temperature of 298.15 K and atmospheric pressure are presented for a set of 20 binary mixtures comprised of the first four propyl esters, C{sub u-1}H{sub 2u-1}COOC{sub 3}H{sub 7} (u = 1 to 4), and five {alpha},{omega}-dichloroalkanes, ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl (v = 2 to 6). All the mixtures are exothermic except for those corresponding to propyl methanoate with v {>=} 4. The V{sub m}{sup E} are positive in most mixtures except for those where v = 4, 5, 6, for V{sub m}{sup E}<0. There is a regular rise in H{sub m}{sup E} with v, while the increase in u produces a greater exothermicity in the mixing process, which becomes inverted for propyl butanoate. The variation in V{sub m}{sup E} with the chain length of the compounds of the mixtures studied is not regular since both the enthalpic and the volumetric effects are due to interactions of different nature, positive and negative. Interpretation of the behavior was assisted by applying the quantum-chemistry method COSMO-RS. This method describes qualitatively and quantitatively the contribution of the different types of interactions, electrostatic, van der Waals, and those due to the (Cl, Cl) bond in the dihalide, and the influence of the ester and dichloroalkane chains. This information was also useful to adequately modify the application of the UNIFAC group contribution model, proposing parameters for the Cl, Cl/carboxylate interaction that vary with the chain length of the compounds involved. With this modification, the results estimated by UNIFAC model can be considered good.

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

KAUST Repository

Spanopoulos, Ioannis

2015-12-22

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

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

KAUST Repository

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

2015-01-01

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

A Raman spectroscopic study of the structural aspects of K2MgCl4 and Cs2MgCl4 as solid single crystals and molten salts

International Nuclear Information System (INIS)

Brooker, M.H.

1975-01-01

Polarized Raman spectra have been obtained for oriented single crystals of K 2 MgCl 4 and Cs 2 MgCl 4 at 77 and 298 K. The data are in excellent agreement with factor group analyses based on the space groups I 4 /mmm (D 17 4 /subh/) and Pnma (D 16 2 /subh/) for the K 2 MgCl 4 and Cs 2 MgCl 4 crystals. In K 2 MgCl 4 the magnesium is surrounded by six chloride ions in a distorted octahedral arrangement with a network structure such that neighboring octahedra share corners. In Cs 2 MgCl 4 a discrete tetrahedral MgCl 4 2- species is present. The 35 Cl-- 37 Cl isotopic splitting of the symmetric stetching mode of the tetrahedral MgCl 4 2- species has been resolved at 77 K and is similar to that observed for CCl 4 . Raman spectra for the high temperature solids and molten salts suggest that the coordination number of magnesium changes from six in solid K 2 MgCl 4 to four in the melt, whereas Cs 2 MgCl 4 melts with retention of the MgCl 4 2- tetrahedral complex. Additional evidence is presented to support previous reports that the MgCl 4 2- tetrahedral species is the principal complex ion in the melts, although a fraction of the magnesium appears to be present in a polynuclear complex, perhaps Mg 2 Cl 6 2-

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

Science.gov (United States)

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

2012-12-01

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

CO2 and CH4 fluxes and carbon balance in the atmospheric interaction of boreal peatlands

International Nuclear Information System (INIS)

Alm, J.

1997-01-01

Release of CO 2 from peat was studied using IR analyzer in a range of boreal peatlands under varying nutrient status and moisture conditions. Root associated CO 2 efflux was separated from the total release by experiments both in the field and in a greenhouse. Emissions of CO 2 and CH 4 (the latter by gas chromatography) were measured during the snow-covered period and their contribution to the annual fluxes of these gases was inspected. Ecosystem exchange of CO 2 under varying irradiation, temperature and moisture conditions was measured at different microsites at two peatland sites with different nutrient ecology. One site represented minerotrophic conditions during a wet growing season and the other site ombrotrophic conditions during an exceptionally dry growing season. Annual carbon balances were compiled for the two sites, and the role of the microsites in the annual carbon balance and CH 4 release was studied. The Holocene history of CO 2 sequestration and CH 4 emission dynamics in a raised mire were simulated using lateral and vertical growth rates derived from radiocarbon ages of peat samples from mire bottom and vertical cores. The model was formulated for a geographic information system (GIS). Artificial or natural lowering of water table increased CO 2 release from peat. A drought lasting from late May to July caused a 90 g C m 2 net loss in the annual C balance of a natural ombrotrophic bog. In drained forested sites the increase in peat CO 2 release could be even 100 %, but the development of the tree layer at least partially compensated for these losses. Wet conditions induced a net accumulation of 67 g C m -2 a -1 in the minerotrophic fen site, while the long term average accumulation rate is estimated to be only 15 g C m -2 a -1 for Finnish fens. Carbon balance in boreal peatlands is thus extremely sensitive to year-to-year climatic variations. Root activity of vascular plants contributed to the total peat CO 2 efflux by 10-40 % as root respiration

Phase formation in Na2MoO4 - MgMoO4 - Cr2(MoO4)3 system

International Nuclear Information System (INIS)

Kotova, I.Yu.; Kozhevnikova, N.M.

1998-01-01

Interaction within Na 2 MoO 4 - MgMoO 4 - Cr 2 (MoO 4 ) 3 ternary system is studied by X ray phase and DTA methods. State diagram of NaCr(MoO 4 ) 2 - MgMoO 4 section is plotted. Production of ternary molybdates of Na 1-x Mg 1-x Cr 1+x (MoO 4 ) 3 , where 0 ≤ x ≤ 0.3, and NaMg 3 Cr(MoO 4 ) 5 composition is ascertained [ru

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

PENGARUH WAKTU KONTAK TERHADAP DAYA ADSORPSI KARBON AKTIF PADA PROSES PURIFIKASI CH4 DARI BIOGAS

Directory of Open Access Journals (Sweden)

Nani Harihastuti

2016-11-01

Full Text Available ABSTRAK Penggunaan biogas sebagai bahan bakar secara langsung sering menimbulkan permasalahan yaitu terjadi bau tidak sedap, peralatan logam  dan kompor cepat berkarat, dinding dapur terkikis  dan api sering  padam sendiri. Hal ini disebabkan dalam biogas selain metana (CH4 terkandung gas-gas lain H2S, NH3, CO2, H2 , CO dan uap air (H2O. Beberapa gas yang bersifat impurities ( H2S, NH3, CO2 dan uap air /H2O akan menurunkan nilai kalori dari biogas dan merugikan lingkungan dan kesehatan. Tujuan dari penelitian ini adalah untuk menghilangkan gas impurities dari biogas melalui proses purifikasi sehingga diperoleh biogas yang mempunyai nilai kalor tinggi dan ramah lingkungan.Metode yang dilakukan dengan proses adsorpsi menggunakan  adsorben karbon aktif dengan variabel waktu kontak, untuk mendapatkan daya adsorpsi yang optimum dari karbon aktif terhadap gas impurities yang ada dalam biogas. Hasil penelitian ini diperoleh data- data              penghilangan / reduksi gas  impuritis H2S mencapai 99,99% , dari 4200 ppm menjadi 0,22 ppm, penghilangan gas NH3 mencapai 94,96%, dari 12,7 ppm menjadi 0,65 ppm, penghilangan gas CO2 mencapai 77,48 %, dari 30, 77 % menjadi 6,93 %, penghilangan uap air (H2O mencapai 97,95%,  dari 0,584 mg/lt menjadi 0,012 mg/lt.Kenaikan konsentrasi methane (CH4 dari 38,2 % menjadi 84,12 %. Hasil purifikasi metana (CH4 dari biogas ini merupakan sumber energi  terbarukan yang aman dan  ramah lingkungan serta dapat di kembangkan lagi penerapannya di IKM tahu lainnya. Waktu jenuh adsorben karbon aktif diperoleh setelah  48 jam proses purifikasi berlangsung. Daya adsorpsi Karbon aktif optimum terhadap masing masing komponen gas impuritis adalah sebagai berikut terhadap H2S adalah  10,98 mg H2S/gram karbon aktif/menit, terhadap NH3  adalah 0,016 mg NH3/gram karbon aktif/menit, terhadap CO2 adalah 0,090mg CO2/gram karbon aktif/menit.Dampak yang terjadi bila biogas tidak dimanfaatkan dan dibiarkan terlepas ke

Experimental confirmation of the Jahn-Teller distortion of CH4+

International Nuclear Information System (INIS)

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

1979-01-01

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

Sono-synthesis and characterization of bimetallic Ni-Co/Al2O3-MgO nanocatalyst: Effects of metal content on catalytic properties and activity for hydrogen production via CO2 reforming of CH4.

Science.gov (United States)

Abdollahifar, Mozaffar; Haghighi, Mohammad; Babaluo, Ali Akbar; Talkhoncheh, Saeed Khajeh

2016-07-01

Sono-dispersion of Ni, Co and Ni-Co over Al2O3-MgO with Al/Mg ratio of 1.5 was prepared and tested for dry reforming of methane. The samples were characterized by XRD, FESEM, PSD, EDX, TEM, BET and FTIR analyses. In order to assess the effect of ultrasound irradiation, Ni-Co/Al2O3-MgO with Co content of 8% prepared via sonochemistry and impregnation methods. The sono-synthesized sample showed better textural properties and higher activity than that of impregnated one. Comparison of XRD patterns indicated that the NiO peaks became broader by increasing Co content over the support. The FESEM images displayed the particles are small and well-dispersed as a result of sonochemistry method. Also, EDX analysis demonstrated better dispersion of Ni and Co as a result of sonochemistry method in confirmation of XRD analysis. The sono-synthesized Ni-Co/Al2O3-MgO as a superior nanocatalyst with Co content of 3% illustrates much higher conversions (97.5% and 99% for CH4 and CO2 at 850 °C), yields (94% and 96% for H2 and CO at 850 °C) and 0.97 of H2/CO molar ratio in all samples using an equimolar feed ratio at 850 °C. During the 1200 min stability test, H2/CO molar ratio remained constant for the superior nanocatalyst. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Directory of Open Access Journals (Sweden)

R. B. Rios

2013-12-01

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

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

DEFF Research Database (Denmark)

Christensen, TR; Panikov, N; Mastepanov, M

2003-01-01

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

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

Science.gov (United States)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

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

Science.gov (United States)

Banks, Simon T; Clary, David C

2009-01-14

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

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

Science.gov (United States)

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

2016-12-01

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

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

Science.gov (United States)

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

2016-12-01

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

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

International Nuclear Information System (INIS)

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

2004-01-01

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

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

AirCore-HR: a high-resolution column sampling to enhance the vertical description of CH4 and CO2

Directory of Open Access Journals (Sweden)

O. Membrive

2017-06-01

Full Text Available An original and innovative sampling system called AirCore was presented by NOAA in 2010 (Karion et al., 2010. It consists of a long (>  100 m and narrow (<  1 cm stainless steel tube that can retain a profile of atmospheric air. The captured air sample has then to be analyzed with a gas analyzer for trace mole fraction. In this study, we introduce a new AirCore aiming to improve resolution along the vertical with the objectives to (i better capture the vertical distribution of CO2 and CH4, (ii provide a tool to compare AirCores and validate the estimated vertical resolution achieved by AirCores. This (high-resolution AirCore-HR consists of a 300 m tube, combining 200 m of 0.125 in. (3.175 mm tube and a 100 m of 0.25 in. (6.35 mm tube. This new configuration allows us to achieve a vertical resolution of 300 m up to 15 km and better than 500 m up to 22 km (if analysis of the retained sample is performed within 3 h. The AirCore-HR was flown for the first time during the annual StratoScience campaign from CNES in August 2014 from Timmins (Ontario, Canada. High-resolution vertical profiles of CO2 and CH4 up to 25 km were successfully retrieved. These profiles revealed well-defined transport structures in the troposphere (also seen in CAMS-ECMWF high-resolution forecasts of CO2 and CH4 profiles and captured the decrease of CO2 and CH4 in the stratosphere. The multi-instrument gondola also carried two other low-resolution AirCore-GUF that allowed us to perform direct comparisons and study the underlying processing method used to convert the sample of air to greenhouse gases vertical profiles. In particular, degrading the AirCore-HR derived profiles to the low resolution of AirCore-GUF yields an excellent match between both sets of CH4 profiles and shows a good consistency in terms of vertical structures. This fully validates the theoretical vertical resolution achievable by AirCores. Concerning CO2 although a

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

International Nuclear Information System (INIS)

Tan, Yee Seng; Halim, Siti Nadiah Abdul; Tiekink, Edward R.T.; Sunway Univ., Bandar Sunway

2016-01-01

Crystallization of Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 from ethanol yields the coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 }.EtOH] ∞ (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ 2 κ 2 -tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ 2 κ 2 -tridentate as for 1 but the other two being κ 2 -chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 3 .MeCN] ∞ and binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2H 2 O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 :2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH 2 (CH 2 CH 2 OH)] 4 [SO 4 ] 2 {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 (4) and the salt [iPrNH 2 (CH 2 CH 2 OH)]{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 3 } (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

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

Directory of Open Access Journals (Sweden)

Reza Abedini

2014-10-01

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

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.

Depth-dependent and surface damages in MgAl sub 2 O sub 4 and MgO irradiated with energetic iodine ions

CERN Document Server

Aruga, T; Ohmichi, T; Okayasu, S; Kazumata, Y; Jitsukawa, S

2002-01-01

Samples of polycrystalline ceramics of MgAl sub 2 O sub 4 irradiated at the ambient temperature with 85 MeV I sup 7 sup + iodine ions to doses up to 1x10 sup 1 sup 9 m sup - sup 2 is observed to be amorphized up to depths around 6 mu m from the ion-incident surface for a dose of 1.2x10 sup 1 sup 9 m sup - sup 2 , through a cross-sectional transmission electron microscopy. A step height of 1 mu m is formed across the border between the masked and irradiated regions of the surface. The height of the step is observed to increase sharply from the irradiated area towards the edge at the border, forming a peak as tall as 1.5 mu m. A glossy, silver-gray film with a thickness less than 0.1 mu m is unexpectedly observed to have formed on the surface of samples of MgAl sub 2 O sub 4 and MgO, in about 3.5 years aging after the irradiation to 1.2x10 sup 1 sup 9 m sup - sup 2 , being left untouched in the air. The film is easily peeled off along grain boundaries and found to be amorphous from the electron diffraction patt...

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

Science.gov (United States)

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

2017-10-01

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

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

CERN Document Server

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

2002-01-01

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

Thermodynamic stability and guest distribution of CH4/N2/CO2 mixed hydrates for methane hydrate production using N2/CO2 injection

International Nuclear Information System (INIS)

Lim, Dongwook; Ro, Hyeyoon; Seo, Yongwon; Seo, Young-ju; Lee, Joo Yong; Kim, Se-Joon; Lee, Jaehyoung; Lee, Huen

2017-01-01

Highlights: • We examine the thermodynamic stability and guest distribution of CH 4 /N 2 /CO 2 mixed hydrates. • Phase equilibria of the CH 4 /N 2 /CO 2 mixed hydrates were measured to determine the thermodynamic stability. • The N 2 /CO 2 ratio of the hydrate phase is almost constant despite the enrichment of CO 2 in the hydrate phase. • 13 C NMR results indicate the preferential occupation of N 2 and CO 2 in the small and large cages of sI hydrates, respectively. - Abstract: In this study, thermodynamic stability and cage occupation behavior in the CH 4 – CO 2 replacement, which occurs in natural gas hydrate reservoirs by injecting flue gas, were investigated with a primary focus on phase equilibria and composition analysis. The phase equilibria of CH 4 /N 2 /CO 2 mixed hydrates with various compositions were measured to determine the thermodynamic stability of gas hydrate deposits replaced by N 2 /CO 2 gas mixtures. The fractional experimental pressure differences (Δp/p) with respect to the CSMGem predictions were found to range from −0.11 to −0.02. The composition analysis for various feed gas mixtures with a fixed N 2 /CO 2 ratio (4.0) shows that CO 2 is enriched in the hydrate phase, and the N 2 /CO 2 ratio in the hydrate phase is independent of the feed CH 4 fractions. Moreover, 13 C NMR measurements indicate that N 2 molecules preferentially occupy the small 5 12 cages of sI hydrates while the CO 2 molecules preferentially occupy the large 5 12 6 2 cages, resulting in an almost constant area ratio of CH 4 molecules in the large to small cages of the CH 4 /N 2 /CO 2 mixed hydrates. The overall experimental results provide a better understanding of stability conditions and guest distributions in natural gas hydrate deposits during CH 4 – flue gas replacement.

TL and OSL studies of carbon doped magnesium aluminate (MgAl2O4:C)

Science.gov (United States)

Raj, Sanu S.; Mishra, D. R.; Soni, Anuj; Grover, V.; Polymeris, G. S.; Muthe, K. P.; Jha, S. K.; Tyagi, A. K.

2016-10-01

The MgAl2O4:C has been synthesized by using two different methods by electron gun and vacuum assisted melting of MgAl2O4 in presence of graphite. The MgAl2O4:C phosphor thus developed by these two different methods have similar types of the TL/OSL defects with multiple overlapping TL glow peaks from 100 °C to 400 °C. The Computerized Curve De-convolution Analysis (CCDA) has been used to measure TL parameters such as thermal trap depth, frequency factor and order of kinetic associated with charge transfer process in TL phenomenon. The investigated TL/OSL results show that these two methods of incorporating carbon in MgAl2O4 have generated closely resemble the defects of similar types in MgAl2O4:C lattice. However, the MgAl2O4:C synthesized by electron gun shows relatively larger concentration of the TL/OSL defects as compared to MgAl2O4:C synthesized using vacuum assisted melting method. The photo-ionization cross-section (PIC) associated with fastest OSL component of MgAl2O4: C is found to be ∼ 0.5 times than that of fastest OSL component of commercially available dosimetric grade α-Al2O3:C. The MgAl2O4:C thus developed shows good dynamic OSL dose linearity from few mGy to 1 Gy. This work reveals that MgAl2O4:C could be developed as potential tissue equivalent OSL / TL material.

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

Science.gov (United States)

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

2018-04-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-11-17

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

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.

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

DEFF Research Database (Denmark)

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

2014-01-01

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

Promising monolayer membranes for CO{sub 2}/N{sub 2}/CH{sub 4} separation: Graphdiynes modified respectively with hydrogen, fluorine, and oxygen atoms

Energy Technology Data Exchange (ETDEWEB)

Zhao, Lianming, E-mail: lmzhao@upc.edu.cn; Sang, Pengpeng; Guo, Sheng; Liu, Xiuping; Li, Jing; Zhu, Houyu; Guo, Wenyue, E-mail: wyguo@upc.edu.cn

2017-05-31

Graphical abstract: Graphdiyne monolayer membrane modified by fluorine or oxygen can effectively separate CO{sub 2}/N{sub 2}/CH{sub 4} mixtures. - Highlights: • Three graphdiyne-like membranes were designed and their stabilities were confirmed. • The DFT and MD results claimed a tunable gas separation property of the membranes. • Graphdiyne modified with F or O can effectively separate CO{sub 2}/N{sub 2}/CH{sub 4} mixtures. - Abstract: Three graphdiyne-like monolayers were designed by substituting one-third diacetylenic linkages with heteroatoms hydrogen, fluorine, and oxygen (GDY-X, X = H, F, and O), respectively. The CO{sub 2}/N{sub 2}/CH{sub 4} separation performance of the designed graphdiyne-like monolayers was investigated by using both first-principle density functional theory (DFT) and molecular dynamic (MD) simulations. The stabilities of GDY-X monolayers were confirmed by the calculated cohesive energies and phonon dispersion spectra. Both the DFT and MD calculations demonstrated that although the GDY-H membrane has poor selectivity for CO{sub 2}/N{sub 2}/CH{sub 4} gases, the GDY-F and GDY-O membranes can excellently separate CO{sub 2} and N{sub 2} from CH{sub 4} in a wide temperature range. Moreover, the CO{sub 2}/N{sub 2} mixture can be effectively separated by GDY-O at temperatures lower than 300 K. Based on the kinetic theory, extremely high permeances were found for CO{sub 2} and N{sub 2} passing through the GDY-X membranes (10{sup −4}–10{sup −2} mol/m{sup 2} s Pa at 298 K). In addition, the influence of relative concentration on selectivity was also investigated for gases in the binary mixtures. This work provides an effective way to modify graphdiyne for the separation of large molecular gases, which is quite crucial in the gas separation industry.

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

Science.gov (United States)

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

2018-02-01

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

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

Science.gov (United States)

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

2018-04-16

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

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

Science.gov (United States)

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

2000-01-01

The BOREAS TGB-1 team made numerous measurements of trace gas concentrations and fluxes at various NSA sites. This data set contains methane (CH4) and carbon dioxide (CO2) concentrations in soil profiles from the NSA-OJP, NSA-OBS, NSA-YJP, and NSA-BP sites during the period of 23-May to 20-Sep-1994. The soil gas sampling profiles of CH 4 and CO 2 were completed to quantify controls on CO2 and CH4 fluxes in the boreal forest. The data are provided in tabular ASCII files.

A cool-temperate young larch plantation as a net methane source - A 4-year continuous hyperbolic relaxed eddy accumulation and chamber measurements

Science.gov (United States)

Ueyama, Masahito; Yoshikawa, Kota; Takagi, Kentaro

2018-07-01

Upland forests are thought to be methane (CH4) sinks due to oxidation by methanotrophs in aerobic soils. However, CH4 budget for upland forests are not well quantified at the ecosystem scale, when possible CH4 sources, such as small wet areas, exists in the ecosystem. Here, we quantified CH4 fluxes in a cool-temperate larch plantation based on four-year continuous measurements using the hyperbolic relaxed eddy accumulation (HREA) method and dynamic closed chambers with a laser-based analyzer. After filling data gaps for half-hourly data using machine-learning-based regressions, we found that the forest acted as a net CH4 source at the canopy scale: 30 ± 11 mg CH4 m-2 yr-1 in 2014, 56 ± 8 mg CH4 m-2 yr-1 in 2015, 154 ± 5 mg CH4 m-2 yr-1 in 2016, and 132 ± 6 mg CH4 m-2 yr-1 in 2017. Hotspot emissions from the edge of the pond could strongly contribute to the canopy-scale emissions. The magnitude of the hotspot emissions was 10-100 times greater than the order of the canopy-scale and chamber-based CH4 fluxes at the dry soils. The high temperatures with wet conditions stimulated the hotspot emissions, and thus induced canopy-scale CH4 emissions in the summer. Understanding and modeling the dynamics of hotspot emissions are important for quantifying CH4 budgets of upland forests. Micrometeorological measurements at various forests are required for revisiting CH4 budget of upland forests.

Agricultural peatland restoration: effects of land-use change on greenhouse gas (CO2 and CH4) fluxes in the Sacramento-San Joaquin Delta.

Science.gov (United States)

Knox, Sara Helen; Sturtevant, Cove; Matthes, Jaclyn Hatala; Koteen, Laurie; Verfaillie, Joseph; Baldocchi, Dennis

2015-02-01

Agricultural drainage of organic soils has resulted in vast soil subsidence and contributed to increased atmospheric carbon dioxide (CO2) concentrations. The Sacramento-San Joaquin Delta in California was drained over a century ago for agriculture and human settlement and has since experienced subsidence rates that are among the highest in the world. It is recognized that drained agriculture in the Delta is unsustainable in the long-term, and to help reverse subsidence and capture carbon (C) there is an interest in restoring drained agricultural land-use types to flooded conditions. However, flooding may increase methane (CH4) emissions. We conducted a full year of simultaneous eddy covariance measurements at two conventional drained agricultural peatlands (a pasture and a corn field) and three flooded land-use types (a rice paddy and two restored wetlands) to assess the impact of drained to flooded land-use change on CO2 and CH4 fluxes in the Delta. We found that the drained sites were net C and greenhouse gas (GHG) sources, releasing up to 341 g C m(-2) yr(-1) as CO2 and 11.4 g C m(-2) yr(-1) as CH4. Conversely, the restored wetlands were net sinks of atmospheric CO2, sequestering up to 397 g C m(-2) yr(-1). However, they were large sources of CH4, with emissions ranging from 39 to 53 g C m(-2) yr(-1). In terms of the full GHG budget, the restored wetlands could be either GHG sources or sinks. Although the rice paddy was a small atmospheric CO2 sink, when considering harvest and CH4 emissions, it acted as both a C and GHG source. Annual photosynthesis was similar between sites, but flooding at the restored sites inhibited ecosystem respiration, making them net CO2 sinks. This study suggests that converting drained agricultural peat soils to flooded land-use types can help reduce or reverse soil subsidence and reduce GHG emissions. © 2014 John Wiley & Sons Ltd.

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.

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

Directory of Open Access Journals (Sweden)

Tingting Li

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

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

Science.gov (United States)

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

2013-04-01

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

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.

[Characteristics of N2, N2O, NO, CO2 and CH4 Emissions in Anaerobic Condition from Sandy Loam Paddy Soil].

Science.gov (United States)

Cao, Na; Wang, Rui; Liao, Ting-ting; Chen, Nuo; Zheng, Xun-hua; Yao, Zhi-sheng; Zhang, Hai; Butterbach-Bahl, Klaus

2015-09-01

Understanding the characteristics of the production of nitrogen gases (N2, N2O and NO), CO2 and CH4 in anaerobic paddy soils is not only a prerequisite for an improved mechanistic understanding of key microbial processes involved in the production of atmospheric greenhouse gases (GHG), but might also provide the basis for designing greenhouse gas mitigation strategies. Moreover, quantifying the composition fractions of denitrification gaseous products is of key importance for improving parameterization schemes of microbial processes in process-oriented models which are increasingly used for assessing soil GHG emissions at site and national scales. In our experiments we investigated two sandy loam soils from two paddy fields. The initial concentrations of soil nitrate and dissolved organic carbon (DOC) were set at approximately 50 mg.kg-1 and mg.kg-1, respectively, by adding a mixture solution of KNO3 and glucose. The emissions of N2, N2O NO, CO2 and CH4, as well as concentrations of carbon and nitrogen substrates for each soil sample were measured simultaneously, using a gas-flow-soil-core technique and a paralleling substrate monitoring system. The results showed that the accumulative emissions of N2, N2O and NO of the two soil samples for the entire incubation period were 6 - 8, 20, and 15 - 18 mg.kg-1, respectively. By measuring the cumulative emissions of denitrification gases (N, = N2 + N2O + NO) we were able to explain 95% to 98% of observed changes in s1ifr nilrate concentrations. The mass fractions of N2, N2O and NO emissions to Nt were approximately 15% -19%, 47% -49%, and 34% -36%, respectively. Thus, in our experiments N2O and NO were the main products of denitrification for the entire incubation period. However, as the temporal courses of hourly or daily production of the denitrification gases showed, NO production dominated and peaked firstly, and then N2O, before finally N2 became the dominant product. Our results show the high temporal dynamic of

Photocatalytic degradation of methylene blue on magnetically separable MgFe2O4 under visible light irradiation

International Nuclear Information System (INIS)

Shahid, Muhammad; Jingling, Liu; Ali, Zahid; Shakir, Imran; Warsi, Muhammad Farooq; Parveen, Riffat; Nadeem, Muhammad

2013-01-01

A magnetically separable single-phase MgFe 2 O 4 photocatalyst with a spinel crystal structure was synthesized by using the solid-state reaction method. The formation of spinel structure is confirmed by X-ray diffraction and Fourier transform infrared spectroscopy. The magnetic measurements showed that the photocatalyst material can be separated from water when an external magnetic field is added and redispersed into water solution after the external magnetic field is eliminated. It is one of the promising photocatalysts for waste water treatment. The photocatalytic activity of MgFe 2 O 4 was investigated by using the photo-decomposition of methylene blue dye under visible light. The photoelectrochemical property of the MgFe 2 O 4 was studied by measuring their photocurrent–potential behavior in 1 M NaOH electrolyte under AM 1.5100 mW cm −2 illumination. - Graphical abstract: Highly efficient magnetically separable MgFe 2 O 4 photocatalyst for organic based impurities decomposition as well as for the production of H 2 gas was synthesized and characterized successfully (a) MgFe 2 O 4 photocatalyst in polluted water, (b) The photocatalyst (MgFe 2 O 4 ) is being attracted toward magnetic field for separation, (c) Hysteresis loop of MgFe 2 O 4 showing magnetic behavior. Highlights: ► New photocatalyst working in the visible range have been synthesized by facile cheap route. ► MgFe 2 O 4 photocatalyst showed well defined magnetically separable behavior. ► Excellent water splitting characteristics to produce H 2 was observed under visible light irradiation

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

Science.gov (United States)

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

2016-07-14

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

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).

Comparing the Electrochemical Performance of LiFePO4/C Modified by Mg Doping and MgO Coating

Directory of Open Access Journals (Sweden)

Jianjun Song

2013-01-01

Full Text Available Supervalent cation doping and metal oxide coating are the most efficacious and popular methods to optimize the property of LiFePO4 lithium battery material. Mg-doped and MgO-coated LiFePO4/C were synthesized to analyze their individual influence on the electrochemical performance of active material. The specific capacity and rate capability of LiFePO4/C are improved by both MgO coating and Mg doping, especially the Mg-doped sample—Li0.985Mg0.015FePO4/C, whose discharge capacity is up to 163 mAh g−1, 145.5 mAh g−1, 128.3 mAh g−1, and 103.7 mAh g−1 at 1 C, 2 C, 5 C, and 10 C, respectively. The cyclic life of electrode is obviously increased by MgO surface modification, and the discharge capacity retention rate of sample LiFePO4/C-MgO2.5 is up to 104.2% after 100 cycles. Comparing samples modified by these two methods, Mg doping is more prominent on prompting the capacity and rate capability of LiFePO4, while MgO coating is superior in terms of improving cyclic performance.

Combustion, performance, and selective catalytic reduction of NOx for a diesel engine operated with combined tri fuel (H_2, CH_4, and conventional diesel)

International Nuclear Information System (INIS)

Abu-Jrai, Ahmad M.; Al-Muhtaseb, Ala'a H.; Hasan, Ahmad O.

2017-01-01

In this study, the effect of tri fuel (ULSD, H_2, and CH_4) operation under real exhaust gas conditions with different gaseous fuel compositions on the combustion characteristics, engine emissions, and selective catalytic reduction (SCR) after treatment was examined at low, medium, and high engine loads. Pt/Al_2O_3-SCR reactor was used and operated at different exhaust gas temperatures. Results revealed that at low load, the two gaseous fuels (H_2 and CH_4) have the same trend on combustion proccess, where both reduce the in-cylinder pressure and rate of heat release. At the high engine load there was a considerable influence appeared as an increase of the premixed combustion phase and a significant decrease of the total combustion duration. In terms of emissions, it was observed that at high engine load, fuels with high CH_4 content tend to reduce NOx formation, whereas, fuels with high H_2 content tend to reduce PM formation, moreover, combustion of tri fuel with 50:50 fuel mixture resulted in lower BSFC compared to the other ratios and hence, the best engine efficiency. The hydrocarbon-SCR catalyst has shown satisfactory performance in NOx reduction under real diesel exhaust gas in a temperature window of 180–280 °C for all engine loads. - Highlights: • Effect of tri fuel (ULSD, H_2, CH_4) on combustion and engine emissions was examined. • Fuel with high CH_4 content (H50-M50 and H25-M75) tend to reduce NOx formation. • Fuel with high H_2 content (H75-M25 and H50-M50) tend to reduce PM formation. • Increasing the percentage of H_2 in the feed gas improved the NO_x reduction. • The hydrocarbon-SCR catalyst has shown satisfactory performance in NO_x reduction.

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