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  • Springer  (32)
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  • 1
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; strontium hydroxyapatite ; lead hydroxyapatite ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of methane has been investigated on lead hydroxyapatite (PbHAp), strontium hydroxyapatite (SrHAp) and their binary mixtures at 873 K. PbHAp showed no activity for the oxidation of methane, while SrHAp produced carbon monoxide selectively at 2–4% conversion. On binary mixtures of the hydroxyapatites the conversion of methane and the selectivity to C2 compounds reached values higher than those of the separate constituents of the mixture. With tetrachloromethane in the feed stream a similar synergistic effect was observed with conversions of methane and selectivities to CH3Cl higher on the binary mixtures than those on either SrHAp or PbHAp. The strontium-containing hydroxyapatite appears to play a crucial role in the activation of methane, while the presence of the lead-containing analogue is apparently required for the minimization of undesirable processes involving methyl radicals.
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  • 2
    ISSN: 1572-879X
    Keywords: methane ; dehydrocondensation ; benzene ; ethylene ; Re catalyst ; HZSM‐5
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new family of rhenium‐based catalysts bearing HZSM‐5 zeolite exhibits remarkable performances for the catalytic dehydrocondensation of methane with CO/CO2 towards ethylene, benzene, and naphthalene in high selectivity of above 90% at 1–3 atm and 973–1023 K. In contrast to Mo/HZSM‐5 catalysts, the EXAFS and TG/DTA/Mass studies reveal that the metallic Re on HZSM‐5 zeolite is a catalytically active and stable phase for the reaction.
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  • 3
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    Catalysis letters 57 (1999), S. 109-113 
    ISSN: 1572-879X
    Keywords: superacid ; zirconia ; molybdenum oxide ; methane ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO3/ZrO2 compares favourably with ZrxCe1-xO2 for methane combustion. The presence of MoO3 is observed to stabilise the tetragonal polymorph of ZrO2 and, as Mo content is increased, dispersed MoO3 crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO3 monolayer during reaction may be of importance.
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  • 4
    ISSN: 1572-879X
    Keywords: methane ; synthesis gas ; dry reforming ; transition metal carbides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The group V and VI transition metal carbides have been prepared by CH4 TPR, and tested for the dry reforming of methane with carbon dioxide, at elevated pressure. Mo2C and WC were the most stable catalysts, while the group V metal carbides showed the stability order: vanadium $${\text{ 〉}}$$ niobium $${\text{ 〉}}$$ tantalum. Catalyst deactivation was due to carbide oxidation with CO2, while stability was associated with the reaction of metal oxide (from deactivation) with CH4, giving the metal carbide. Calculation of the Gibbs free energy for this reaction resulted in a predicted catalyst stability trend similar to that obtained experimentally.
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  • 5
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    Catalysis letters 58 (1999), S. 123-125 
    ISSN: 1572-879X
    Keywords: methane ; sulfated zirconia ; ethene ; isobutane ; superacid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In a continuous-flow differential microreactor, sulfated zirconia (SZ), deliberately activated in situ by water, has converted methane at 673 K to a C2–C6 hydrocarbon mixture of which 65–70% was ethene and isobutane. Maximum conversion activity of ∼4.6%, corresponding to 4×104 mole methane reacted per mole sulfate per second, was attainable at S/(added H2O) molar ratio of 3.0 and methane flow rate of 5.6×106 mol (g-SZ)−1 s−1. This methane conversion could be catalytic and may involve superacidic sites.
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  • 6
    ISSN: 1572-879X
    Keywords: La–Cr–O catalyst ; methane ; combustion ; oxygen adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The catalytic activities of methane combustion of La–Cr–O catalysts prepared with and without polyacrylic acid as a template have been compared. The polymer-templated catalyst had a higher BET surface area, 12.3 m2 g−1, than that obtained from the conventional precipitation method, 2.9 m2 g−1. The results of XRD and SEM experiments suggested that the structural characteristics were almost similar. Surprisingly, the areal rate of methane combustion over the catalyst with a small surface area was ten times larger than that of the catalyst with a large surface area. However, the site time yields (STY) based on the oxygen adsorption capacity were similar, independent of the surface area and preparation conditions.
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  • 7
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 8
    ISSN: 1572-879X
    Keywords: combustion ; methane ; palladium catalyst ; zirconia ; water vapor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Combustion of a trace amount of CH4 over Pd catalysts supported on calcined ZrO2 was examined under nearly exhaust gas conditions where the temperature is not so high and water vapor coexists. High catalytic activity was obtained with ZrO2 support calcined at 1073 and 1273 K. The durability test at 673 K for 100 h revealed that the activity of these catalysts hardly decreased, while that of the Pd catalysts supported on calcined Al2O3 were much decreased in the course of time. These results demonstrated the advantages of ZrO2 as a support for Pd catalysts in the present reaction.
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  • 9
    ISSN: 1572-879X
    Keywords: methane ; oxygen ; aromatization ; Mo/HZSM‐5 ; coke formation ; UV‐Raman spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The aromatization of methane over a Mo/HZSM‐5 catalyst was carried out in the presence of oxygen. It is shown that the addition of a small amount of oxygen is beneficial to improve the durability of the catalyst. UV‐Raman spectra disclose that the carbonaceous deposits formed on the HZSM‐5 are mainly polyolefinic and aromatic, while that on the Mo/HZSM‐5 is mainly polyaromatic. The small amount of O2 added may partly remove the coke deposits on the active sites and keep the catalyst as MoOxCy/HZSM‐5, thus resulting in an improvement of the catalytic performance of the Mo/HZSM‐5 catalyst.
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  • 10
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    Plasma chemistry and plasma processing 19 (1999), S. 91-109 
    ISSN: 1572-8986
    Keywords: Microwave plasma ; CARS on methyl ; methane ; hydrogen ; modeling, methane plasma ; electron energy distribution function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Coherent anti-Stokes Raman scattering (CARS) carried out using the BOXCARS technique is applied to quantify the density and temperature of hydrogen, methane, and methyl in a process plasma generated by a surfatron in the pressure range from 30 to 3000 Pa. Below approximately 500 Pa all species and their temperatures have a flat distribution dominated by diffusive processes. At higher pressure the plasma localizes near the inner surface of the surfatron tube. A strong depletion of the methane ground state density is observed, where the gas temperature remains at 400 K on a moderate level. On the other side the methyl density is high at the position of high methane depletion. The measured methyl density is a factor of 200 lower than the methane density, in contrast to the factor 10–20 often reported in the literature. The measured data can be interpreted by proper modeling by means of the Boltzmann equation of electrons, balancing of chemical reactions and diffusive processes. The calculated methane and methyl densities agree with the measured ones only if the electron temperature is assumed to be near 1 eV and thus much lower than predicted in previous papers.
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  • 11
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    Plasma chemistry and plasma processing 19 (1999), S. 395-419 
    ISSN: 1572-8986
    Keywords: Microwave plasma ; plasma chemistry ; methane ; methanol ; laser diagnostics ; TDLAS ; CH3 ; CH2O ; HCOOH
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and ten stable molecules in H2-Ar-O2 microwave plasmas containing up to 7.2% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbons varied between 30 and 90% and the methyl radical concentration was found to be in the range 10 10 –10 12 molecules cm −3 . The methyl radical concentration and the concentrations of the stable C-2 hydrocarbons C 2 H 2 , C 2 H 4 , and C 2 H 6 , produced in the plasma decayed exponentially when increasing amounts of O 2 were added at fixed methane or methanol partial pressures. In addition to detecting the hydrocarbon species, the major products CO, CO 2 , and H 2 O were also monitored. For the first time, formaldehyde, formic acid, and methane were detected in methanol microwave plasmas, formaldehyde was detected in methane microwave plasmas. Chemical modeling with 57 reactions was used to successfully predict the concentrations in methane plasmas in the absence of oxygen and the trends for the major chemical product species as oxygen was added.
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  • 12
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    Plasma chemistry and plasma processing 19 (1999), S. 505-512 
    ISSN: 1572-8986
    Keywords: Corona discharge ; methane ; carbon dioxide ; carbon monoxide ; cold plasma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The conversion of CO 2 and (CH 4+CO 2 ) mixtures to CO, at room temperature and atmospheric pressure conditions, in pulsed corona discharges, was investigated. Conversion of pure CO 2 was 16.8% at 10 cm 3 -min −1 flow rate, which corresponds to 75 μmol-min −1 rate of conversion. The CO 2 conversion was improved to 38% (85 μmol-min −1 by feeding the reactor with CH 4+CO 2 gas mixture (1:1 ratio), simultaneously with CH 4 conversion of 46% (∼102.7 μmol-min −1 ) at 10 cm 3 -min −1 flow rate of feed gases and 9 W power conditions. Rate of CO production is increased from ∼110 to ∼180 μmol-min −1 with the variation of feed gas (CH 4+CO 2 mixture, 1:1 ratio) flow rate from 10 to 40 cm 3 -min −1 at 9W, which corresponds to energy efficiency of 2.5 to 4.1%. Highest energy yield of 25 g/kWh for CH 4 conversion, 29 g/kWh for CO 2 conversion, and 33 g/kWh for CO production were achieved.
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  • 13
    ISSN: 1572-9028
    Keywords: ellipsometry ; carbon monoxide ; methane ; palladium ; palladium oxide ; oxidation ; oscillations ; catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Spectroscopic ellipsometry is used to monitor the surface of a thick Pd‐film catalyst during the oxidation of either carbon monoxide or methane. Dense PdO layers form under sufficiently lean conditions (excess oxygen) for both reactions. A stable metal surface exists in the case of CO, but a very porous PdO layer develops in the case of methane, under rich conditions. There is a large hysteresis in the conditions for PdO formation in the case of CO oxidation. Spontaneous oscillations in catalytic activity and Pd‐surface composition occur for both reactions, the higher activities corresponding to O‐atom‐rich or PdO‐rich surfaces for CO or methane oxidation, respectively.
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  • 14
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    Topics in catalysis 8 (1999), S. 211-222 
    ISSN: 1572-9028
    Keywords: reforming ; methane ; carbon dioxide ; Rh/SiO2 ; vanadia-promoted Rh/SiO2 ; FTIR spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reforming of methane with carbon dioxide over rhodium dispersed on silica, Rh/SiO2, and vanadia-promoted silica, Rh/VOx/SiO2, was studied by kinetic test reactions under differential conditions in a temperature range from 723 to 773 K. Transmission infrared spectroscopy was applied to observe the interaction of CO2 with the catalysts and the formation of surface intermediates during the CO2–CH4 reforming reaction. To analyze carbon deposition XP spectroscopy and TPO was carried out. It has been shown that the promotion of Rh/SiO2 catalysts with vanadium oxide enhances the catalytic activity for CO2 reforming of methane and decreases the deactivation by carbon deposition. This is attributed to the formation of a partial VOx overlayer on the Rh surface, which reduces the size of accessible ensembles of Rh atoms required for coke formation and creates new sites at the Rh–VOx interfacial region that are considered to be active sites for the activation/dissociation of carbon dioxide.
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  • 15
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    Biogeochemistry 47 (1999), S. 15-23 
    ISSN: 1573-515X
    Keywords: ethane ; groundwater ; methane ; propane ; redox ; soil gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract This study investigates the presence and concentration of light hydrocarbon gases in soil vapor located immediately above the capillary fringe of a petroleum-contaminated aquifer. A correlation was observed for the linear regression plot of redox potential versus detectable C2+C3 alkane concentrations for a limited number of sampling points. C2+C3 alkanes were not detected at points were redox potentials in groundwater exceeded --260 millivolts. The predominance of methanogenic processes in this redox range, as well as the observed C2+C3 concentration ratios, suggest that ethane and propane gases in soil vapor may be biogenically produced as well as a result of volatilization from NAPL.
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  • 16
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    Biogeochemistry 47 (1999), S. 15-23 
    ISSN: 1573-515X
    Keywords: ethane ; groundwater ; methane ; propane ; redox ; soil gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract This study investigates the presence and concentration of light hydrocarbon gases in soil vapor located immediately above the capillary fringe of a petroleum-contaminated aquifer. A correlation was observed for the linear regression plot of redox potential versus detectable C2+C3 alkane concentrations for a limited number of sampling points. C2+C3 alkanes were not detected at points were redox potentials in groundwater exceeded -260 millivolts. The predominance of methanogenic processes in this redox range, as well as the observed C2+C3 concentration ratios, suggest that ethane and propane gases in soil vapor may be biogenically produced as well as a result of volatilization from NAPL.
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  • 17
    ISSN: 1573-515X
    Keywords: Atlantic ; ethylene ; methane ; sea-air exchange
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The vertical distributions of ethylene and methane in the upper water column of the subtropical Atlantic were measured along a transect from Madeira to the Caribbean and compared with temperature, salinity, oxygen, nutrients, chlorophyll-a, and dissolved organic carbon (DOC). Methane concentrations between 41.6 and 60.7 nL L−1 were found in the upper 20 m of the water column giving a calculated average flux of methane into the atmosphere of 0.82μg m−2 h−1. Methane profiles reveal several distinct maxima in the upper 500 m of the water column and short-time variations which are presumably partly related to the vertical migration of Zooplankton. Ethylene concentrations in near surface waters varied in the range of 1.8 to 8.2 nL L−1. Calculated flux rates for ethylene into the atmosphere were in the range of 0.41 to 1.35μg m−2 h−1 with a mean of 0.83μg m−2h−2. Maximum concentrations of up to 39.2 nL L−2 were detected directly below the pycnocline in the western Atlantic. The vertical distributions of ethylene generally showed one maximum at the pycnocline (about 100 m depth) where elevated concentrations of chlorophyll-a, dissolved oxygen, and nutrients were also found; no ethylene was detected below 270 m depth. This suggests that ethylene release is mainly related to one, probably phytoplankton associated, source, while for methane, enhanced net production occurs at various depth horizons. For surface waters, a simple correlation between ethylene and chlorophyll-a or DOC concentrations could not be observed. No considerable diurnal variation was observed for the distribution and concentration of ethylene in the upper water column.
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  • 18
    ISSN: 1573-515X
    Keywords: grassland ; methane ; peat ; spatial variability ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Methane (CH4) emissions from soils, representing the consequence of CH4 production, CH4 consumption and CH4 transport, are poorly characterised and show a large spatial variability. This study aimed to assess the determinants of field-scale spatial variability of CH4 emissions from wet grasslands on peat soil. Mean CH4 emission rates of a three-year experiment at 18 plots distributed over three sites in the nature preserve “Nieuwkoopse Plassen” on peat soil in the Netherlands were related to CH4 production and CH4 consumption capacities of soil layers, and to soil and vegetation characteristics. Spatial variability of CH4 emissions and possible determining factors was high. Annual CH4 emissions ranged from 3 to 37 g CH4 m-2 yr-1. Coefficients of variation (CV) of CH4 emissions were on average 37% among sites and 83% within sites. Most important determinants of spatial variability were CH4 production capacity (average: 211 ng CH4 g-1 dry soil h-1; CV: 131%) and aboveground biomass of sedges (Carex spp.) (average: 0.45 g dm-2; CV: 127%) (P 〈 0.01). Sedges may affect CH4 emissions by stimulating CH4 transport from anaerobic layers to the surface via their vascular system and/or by serving as substrate for methanogens. For extrapolation of CH4 emissions to larger areas, best results will be obtained by using factors that are easy to determine, like vegetation.
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  • 19
    ISSN: 1573-515X
    Keywords: grassland ; ground water level ; methane ; peat ; temperature ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The area of wet grasslands on peat soil in the Netherlands is slowly increasing at the expense of drained, agriculturally used grasslands. This study aimed (i) to assess the contribution of wet grasslands on peat soil to methane (CH4) emissions, and (ii) to explain differences among sites and between years in order to improve our understanding of controlling factors. For these purposes, a field study was conducted in the period 1994–1996 in the nature preserve “Nieuwkoopse Plassen”, which is a former peat mining and agricultural area. Net CH4 emissions were measured weekly to monthly with vented closed flux chambers at three representative sites, and at ditches near these sites. Three-years average of CH4 emissions was 7.9 g CH4 m- 2 yr-1 for Drie Berken Zudde, 13.3 for Koole, and 20.4 for Brampjesgat. Ditches near the sites emitted 4.2–22.5 g CH4 m-2 yr-1. The time-course of CH4 emissions for all experimental sites and years was fit with a multiple linear regression model with ground water level and soil temperature as independent variables. Lowering or raising the ground water level by 5 cm could decrease or increase CH4 emissions by 30–50%. Therefore, ground water level management of these grasslands should be done with care.
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  • 20
    ISSN: 1573-515X
    Keywords: climate ; methane ; N2O ; Puerto Rico ; soil oxygen ; soil phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured soil oxygen concentrations at 10 and 35 cm depths and indices of biogeochemical cycling in upland forest soils along a rainfall and elevation gradient (3500–5000 mm y−1; 350–1050 masl) and along topographic gradients (ridge to valley, ∼150 m) in the Luquillo Experimental Forest, Puerto Rico. Along the rainfall gradient, soil O2 availability decreased significantly with increasing annual rainfall, and reached very low levels (〈3%) in individual chambers for up to 25 consecutive weeks over 82 weeks of study. Along localized topographic gradients, soil O2 concentrations were variable and decreased significantly from ridges to valleys. In the valleys, up to 35% of the observations at 10–35 cm depth were 〈3% soil O2. Cross correlation analyses showed that soil O2 concentrations were significantly positively correlated along the topographic gradient, and were sensitive to rainfall and hydrologic output. Soil O2 concentrations in valley soils were correlated with rainfall from the previous day, while ridge sites were correlated with cumulative rainfall inputs over 4 weeks. Soils at the wettest point along the rainfall gradient had very high soil methane concentrations (3–24%) indicating a strong influence of anaerobic processes. We measured net methane emission to the atmosphere at the wettest sites of the rainfall gradient, and in the valleys along topographic gradients. Other measures of biogeochemical function such as soil organic matter content and P availability were sensitive to chronic O2 depletion along the rainfall gradient, but less sensitive to the variable soil O2 environment exhibited at lower elevations along topographic gradients.
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  • 21
    ISSN: 1573-515X
    Keywords: alpine tundra ; methane ; trace gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. InCarex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in oneCarex site (seasonal mean=+8.45 mg CH4 m−2 d−1) was significantly larger than in the otherCarex sites (seasonal means=−0.06 and +0.05 mg CH4 m−2 d−1). This high CH4 flux may have resulted from shallower snowpack during the winter. InAcomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean=−0.43 mg CH4 m−2 d−1). In the windsweptKobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean=−0.77 mg CH4 m−2 d−1). Methane fluxes correlated with a different set of environmental factors within each plant community. In theCarex plant community, CH4 emission was limited by soil temperature. In theAcomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In theKobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.
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  • 22
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    Biogeochemistry 47 (1999), S. 187-202 
    ISSN: 1573-515X
    Keywords: boreal peatland ; floating peat ; methane ; reservoirs ; wetlands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The effect of flooding on methane (CH4) fluxes was studied through the construction of an experimental reservoir in a boreal forest wetland at the Experimental Lakes Area in northwestern Ontario. Prior to flooding, the peatland surface was a small source of CH4 to the atmosphere (1.0 ± SD of 2.3 mg CH4 m−2 d−1). After flooding, CH4 fluxes from the submerged peat surface increased to 64±68 mg CH4 m−2 d−1. CH4 bubbles within the submerged peat caused about 1/3 of the peat to float. Fluxes from these floating peat islands were much higher (440±350 mg CH4 m−2 d−1) than from both the pre-flood (undisturbed) and the post-flood (submerged) peat surfaces. The high fluxes of CH4 from the floating peat surfaces may be explained by a number of factors known to affect the production and consumption of CH4 in peat. In floating peat, however, these factors are particularly enhanced and include decreased oxidation of CH4 due to the loss of aerobic habitat normally found above the water table of undisturbed peat and to increased peat temperatures. The extremely high fluxes associated with newly lifted peat may decrease as the islands age. However, CH4 flux rates from floating peat islands that were several years old still far exceeded those from undisturbed peat surfaces and from the water surface of a newly created reservoir.
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  • 23
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    Biogeochemistry 47 (1999), S. 187-202 
    ISSN: 1573-515X
    Keywords: boreal peatland ; floating peat ; methane ; reservoirs ; wetlands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The effect of flooding on methane (CH4) fluxes was studied through the construction of an experimental reservoir in a boreal forest wetland at the Experimental Lakes Area in northwestern Ontario. Prior to flooding, the peatland surface was a small source of CH4 to the atmosphere (1.0± SD of 2.3 mg CH4 m−2 d−1). After flooding, CH4 fluxes from the submerged peat surface increased to 64±68 mg CH4 m−2 d−1 CH4 bubbles within the submerged peat caused about 1/3 of the peat to float. Fluxes from these floating peat islands were much higher (440±350 mg CH4 m−2 d−2) than from both the pre-flood (undisturbed) and the post-flood (submerged) peat surfaces. The high fluxes of CH4 from the floating peat surfaces may be explained by a number of factors known to affect the production and consumption of CH4 in peat. In floating peat, however, these factors are particularly enhanced and include decreased oxidation of CH4 due to the loss of aerobic habitat normally found above the water table of undisturbed peat and to increased peat temperatures. The extremely high fluxes associated with newly lifted peat may decrease as the islands age. However, CH4 flux rates from floating peat islands that were several years old still far exceeded those from undisturbed peat surfaces and from the water surface of a newly created reservoir.
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  • 24
    ISSN: 1573-515X
    Keywords: alpine tundra ; methane ; trace gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. In Carex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in one Carex site (seasonal mean = +8.45 mg CH4 m-2 d-1) was significantly larger than in the other Carex sites (seasonal means = –0.06 and +0.05 mg CH4 m-2 d-1). This high CH4 flux may have resulted from shallower snowpack during the winter. In Acomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean = –0.43 mg CH4 m-2 d-1). In the windswept Kobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean = –0.77 mg CH4 m-2 d-1). Methane fluxes correlated with a different set of environmental factors within each plant community. In the Carex plant community, CH4 emission was limited by soil temperature. In the Acomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In the Kobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.
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  • 25
    ISSN: 1573-515X
    Keywords: Atlantic ; ethylene ; methane ; sea-air exchange
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The vertical distributions of ethylene and methane in the upper water column of the subtropical Atlantic were measured along a transect from Madeira to the Caribbean and compared with temperature, salinity, oxygen, nutrients, chlorophyll-a, and dissolved organic carbon (DOC). Methane concentrations between 41.6 and 60.7 nL L-1 were found in the upper 20 m of the water column giving a calculated average flux of methane into the atmosphere of 0.82 μg m-2 h-1. Methane profiles reveal several distinct maxima in the upper 500 m of the water column and short-time variations which are presumably partly related to the vertical migration of zooplankton. Ethylene concentrations in near surface waters varied in the range of 1.8 to 8.2 nL L-1. Calculated flux rates for ethylene into the atmosphere were in the range of 0.41 to 1.35 μg m-2 h-1 with a mean of 0.83 μg m-2 h-1. Maximum concentrations of up to 39.2 nL L-1 were detected directly below the pycnocline in the western Atlantic. The vertical distributions of ethylene generally showed one maximum at the pycnocline (about 100 m depth) where elevated concentrations of chlorophyll-a, dissolved oxygen, and nutrients were also found; no ethylene was detected below 270 m depth. This suggests that ethylene release is mainly related to one, probably phytoplankton associated, source, while for methane, enhanced net production occurs at various depth horizons. For surface waters, a simple correlation between ethylene and chlorophyll-a or DOC concentrations could not be observed. No considerable diurnal variation was observed for the distribution and concentration of ethylene in the upper water column.
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  • 26
    ISSN: 1573-515X
    Keywords: carbon dioxide ; gas gradients ; methane ; nitrous oxide ; peatland ; winter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract CO2 and CH4 fluxes during the winter were measured at natural and drained bog and fen sites in eastern Finland using both the closed chamber method and calculations of gas diffusion along a concentration gradient through the snowpack. The snow diffusion results were compared with those obtained by chamber, but the winter flux estimates were derived from chamber data only. CH4 emissions from a poor bog were lower than those from an oligotrophic fen, while both CO2 and CH4 fluxes were higher in the Carex rostrata-occupied marginal (lagg) area of the fen than in the slightly less fertile centre. Average estimated winter CO2-C losses from virgin and drained forested peatlands were 41 and 68 g CO2-C m- 2, respectively, accounting for 23 and 21% of the annual total CO2 release from the peat. The mean release of CH4-C was 1.0 g in natural bogs and 3.4 g m-2 in fens, giving rise to winter emissions averaging to 22% of the annual emission from the bogs and 10% of that from the fens. These wintertime carbon gas losses in Finnish natural peatlands were even greater than reported average long-term annual C accumulation values (less than 25 g C m-2). The narrow range of 10–30% of the proportion of winter CO2 and CH4 emissions from annual emissions found in Finnish peatlands suggest that a wider generalization in the boreal zone is possible. Drained forested bogs emitted 0.3 g CH4-C m-2 on the average, while the effectively drained fens consumed an average of 0.01 g CH4-C m- 2. Reason for the low CH4 efflux or net oxidation in drained peatlands probably lies in low substrate supply and thus low CH4 production in the anoxic deep peat layers. N2O release from a fertilized grassland site in November–May was 0.7 g N2O m-2, accounting for 38% of the total annual emission, while a forested bog released none and two efficiently drained forested fens 0.09 (28% of annual release) and 0.04 g N2O m- 2 (27%) during the winter, respectively.
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  • 27
    ISSN: 1573-515X
    Keywords: carbon dioxide ; gas gradients ; methane ; nitrous oxide ; peatland ; winter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract CO2 and CH4 fluxes during the winter were measured at natural and drained bog and fen sites in eastern Finland using both the closed chamber method and calculations of gas diffusion along a concentration gradient through the snowpack. The snow diffusion results were compared with those obtained by chamber, but the winter flux estimates were derived from chamber data only. CH4 emissions from a poor bog were lower than those from an oligotrophic fen, while both CO2 and CH4 fluxes were higher in theCarex rostrata- occupied marginal (lagg) area of the fen than in the slightly less fertile centre. Average estimated winter CO2-C losses from virgin and drained forested peatlands were 41 and 68 g CO2-C m−2, respectively, accounting for 23 and 21% of the annual total CO2 release from the peat. The mean release of CH4-C was 1.0 g in natural bogs and 3.4 g m−2 in fens, giving rise to winter emissions averaging to 22% of the annual emission from the bogs and 10% of that from the fens. These wintertime carbon gas losses in Finnish natural peatlands were even greater than reported average long-term annual C accumulation values (less than 25g C m−2). The narrow range of 10–30% of the proportion of winter CO2 and CH4 emissions from annual emissions found in Finnish peatlands suggest that a wider generalization in the boreal zone is possible. Drained forested bogs emitted 0.3 g CH4-C m−2 on the average, while the effectively drained fens consumed an average of 0.01 g CH4-C m−2. Reason for the low CH4. efflux or net oxidation in drained peatlands probably lies in low substrate supply and thus low CH4 production in the anoxic deep peat layers. N2O release from a fertilized grassland site in November–May was 0.7 g N2O m−2, accounting for 38% of the total annual emission, while a forested bog released none and two efficiently drained forested fens 0.09 (28% of annual release) and 0.04 g N2O m−2 (27%) during the winter, respectively.
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  • 28
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    Biogeochemistry 44 (1999), S. 205-220 
    ISSN: 1573-515X
    Keywords: grassland ; ground water level ; methane ; peat ; temperature ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The area of wet grasslands on peat soil in the Netherlands is slowly increasing at the expense of drained, agriculturally used grasslands. This study aimed (i) to assess the contribution of wet grasslands on peat soil to methane (CH4) emissions, and (ii) to explain differences among sites and between years in order to improve our understanding of controlling factors. For these purposes, a field study was conducted in the period 1994–1996 in the nature preserve “Nieuwkoopse Plassen”, which is a former peat mining and agricultural area. Net CH4 emissions were measured weekly to monthly with vented closed flux chambers at three representative sites, and at ditches near these sites. Three-years average of CH4 emissions was 7.9 g CH4 m−2 yr−1 for Drie Berken Zudde, 13.3 for Koole, and 20.4 for Brampjesgat. Ditches near the sites emitted 4.2–22.5 g CH4 m−2 yr−1. The time-course of CH4 emissions for all experimental sites and years was fit with a multiple linear regression model with ground water level and soil temperature as independent variables. Lowering or raising the ground water level by 5 cm could decrease or increase CH4 emissions by 30–50%. Therefore, ground water level management of these grasslands should be done with care.
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  • 29
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    Biogeochemistry 44 (1999), S. 221-237 
    ISSN: 1573-515X
    Keywords: grassland ; methane ; peat ; spatial variability ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Methane (CH4) emissions from soils, representing the consequence of CH4 production, CH4 consumption and CH4 transport, are poorly characterised and show a large spatial variability. This study aimed to assess the determinants of field-scale spatial variability of CH4 emissions from wet grasslands on peat soil. Mean CH4 emission rates of a three-year experiment at 18 plots distributed over three sites in the nature preserve “Nieuwkoopse Plassen” on peat soil in the Netherlands were related to CH4 production and CH4 consumption capacities of soil layers, and to soil and vegetation characteristics. Spatial variability of CH4 emissions and possible determining factors was high. Annual CH4 emissions ranged from 3 to 37 g CH4 m−2 yr−1. Coefficients of variation (CV) of CH4 emissions were on average 37% among sites and 83% within sites. Most important determinants of spatial variability were CH4 production capacity (average: 211 ng CH4 g−1 dry soil h−1; CV: 131%) and aboveground biomass of sedges (Carex spp.) (average: 0.45 g dm−2; CV: 127%) (P〈0.01). Sedges may affect CH4 emissions by stimulating CH4 transport from anaerobic layers to the surface via their vascular system and/or by serving as substrate for methanogens. For extrapolation of CH4 emissions to larger areas, best results will be obtained by using factors that are easy to determine, like vegetation.
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  • 30
    ISSN: 1573-515X
    Keywords: climate ; methane ; N2O ; Puerto Rico ; soil oxygen ; soil phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured soil oxygen concentrations at 10 and 35 cm depths and indices of biogeochemical cycling in upland forest soils along a rainfall and elevation gradient (3500–5000 mm y−1; 350–1050 masl) and along topographic gradients (ridge to valley, ∼150 m) in the Luquillo Experimental Forest, Puerto Rico. Along the rainfall gradient, soil O2 availability decreased significantly with increasing annual rainfall, and reached very low levels (〈3%) in individual chambers for up to 25 consecutive weeks over 82 weeks of study. Along localized topographic gradients, soil O2 concentrations were variable and decreased significantly from ridges to valleys. In the valleys, up to 35% of the observations at 10–35 cm depth were 〈3% soil O2. Cross correlation analyses showed that soil O2 concentrations were significantly positively correlated along the topographic gradient, and were sensitive to rainfall and hydrologic output. Soil O2 concentrations in valley soils were correlated with rainfall from the previous day, while ridge sites were correlated with cumulative rainfall inputs over 4 weeks. Soils at the wettest point along the rainfall gradient had very high soil methane concentrations (3–24%) indicating a strong influence of anaerobic processes. We measured net methane emission to the atmosphere at the wettest sites of the rainfall gradient, and in the valleys along topographic gradients. Other measures of biogeochemical function such as soil organic matter content and P availability were sensitive to chronic O2 depletion along the rainfall gradient, but less sensitive to the variable soil O2 environment exhibited at lower elevations along topographic gradients.
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  • 31
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    Reaction kinetics and catalysis letters 66 (1999), S. 381-386 
    ISSN: 1588-2837
    Keywords: Microwave ; methane ; partial oxidation ; syngas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this paper the results of the partial oxidation of methane over Ni-based and Co-based catalysts activated by two different heating modes (conventional and microwaves) are reported. Compared with a conventional heating mode, the temperature of the catalytic bed is much lower and there is a higher selectivity of CO and H2 with microwave irradiation.
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  • 32
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    Reaction kinetics and catalysis letters 68 (1999), S. 183-190 
    ISSN: 1588-2837
    Keywords: Reforming ; methane ; carbon dioxide ; catalyst ; metal oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of basic and rare earth metal oxides on the stability of nickel-based catalysts for the CO2 reforming of CH4 has been studied. The addition of metal oxides increased the stability of Ni-based catalysts and reversed the values of the reaction orders with respect to both CH4 and CO2. In the presence of metal oxides, the values of the reaction orders with respect to CO2 partial pressure followed the same trend of catalyst stability.
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