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  • 2000-2004  (1)
  • 1995-1999  (2)
  • 1975-1979  (6)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 79 (1975), S. 7-11 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 79 (1975), S. 677-681 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Chemical reviews 76 (1976), S. 801-826 
    ISSN: 1520-6890
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Nutrient cycling in agroecosystems 48 (1997), S. 61-68 
    ISSN: 1573-0867
    Keywords: biomass burning ; deforestation ; N-fertilization ; NO soil fluxes ; soil plowing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Changes in land use driven by the increasing demand of food are affecting the fluxes of trace gases to the atmosphere. The more important human activities that affect NO soil fluxes are: deforestation, intensification of agricultural practices, and biomass burning. In this review emphasis is given to identifying the physicochemical and biological processes involved in the changes, and no attempt to quantify their contribution to global or regional NO budgets is made. Conversion of tropical forest to pasture is occurring very rapidly. An increase of the NO emission is observed immediately after deforestation (1–5 years) followed by a significant decrease (below forest levels) in old pastures and secondary successional forests. It seems that deforested tropical areas produce, in the long term, less NO than primary forests. The observed changes are not completely understood, but are most likely driven by the availability of exchangeable nitrogen and the bacteria' population. Soil plowing and fertilization are important factors that affect NO fluxes in agricultural soils. Plowing increases soil porosity and aeration, as well increasing the surface area that is exposed to the atmosphere. These physical changes increase the production of soil nitrate, and the escape efficiency of NO from the soil, enhancing NO fluxes. The emission of NO from fertilized soils depends on many variables: type of fertilizer (i.e. ammonium, nitrate), the structure of the soil microbial community (e.g., populations of nitrifiers and denitrifiers), meteorogical conditions (e.g. soil moisture and temperature), and soil management (e.g. plowing). A combination of these factors should explain the large range reported for the fraction of N-fertilizer that is emitted as NO to the atmosphere. Measurements made in diverse ecosystems show that vegetation burning enhances NO soil emissions. However, it seems that different processes, which are not well understood, occur at the various sites; e.g., in the tropical savannah, enhanced emissions, from dry soils, are observed immediately after burning, whereas in Californian chaparral burned dry soils emit on average less than the unburned plots, and the fluxes only increase after soil wetting. Changes in the physical conditions of the soil surface and N availability are the most likely factors that explain the increased fluxes.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1573-0662
    Keywords: nonmethane hydrocarbons ; isoprene ; tropical atmosphere ; oil field emissions ; potential ozone formation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The levels of low molecular weight hydrocarbons were measured at pristine sites and rural locations affected by hydrocarbon emissions from oil and gas producing fields in Venezuela. At the clean sites, lower concentrations of C2 to C6 alkanes were observed, whereas, in comparison with remotes sites, very much higher levels were measured at the polluted sites. Alkenes present relatively high concentrations, with isoprene being the most abundant, all over the study region. The main sources of alkenes are likely to be natural, mainly from vegetation. The levels of alkanes recorded at the clean sites and the alkene levels found everywhere in the region are in agreement with the values reported for other clean sites in the tropics. The increase of ozone production capacity due to the anthropogenic emissions of alkanes from oil and gas fields was estimated. Due to the presence in the atmosphere of important amounts of naturally emitted isoprene, ethene and propene, which makes a substantial contribution to the reactivity of the hydrocarbon mixture, a small increase (〈5%) was estimated to occur in the capacity of the ozone production at a regional scale during the rainy season.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 35 (2000), S. 249-272 
    ISSN: 1573-0662
    Keywords: ozone ; tropical atmosphere ; boundary layer ozone ; biomass burning ; Venezuelan savannah
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract In recent field campaigns, boundary layer ozone concentrations were measuredat different sites in the Orinoco river basin (mainly savannahs) and nearbylocations (cloud forest and coastal sites), during dry and wet seasons. Theresults provide a comprehensive description of boundary layer ozone in atropical region north of the equator where scarce information is available.Ozone measurements were made using photometric ozone analyzers. In thesavannah region, ozone profiles (up to 1000 m) were also obtained usingelectrochemical concentration cell sondes, launched in a tethered balloon.The results, in comparison with other parts of the world, confirm the lowvalues for the concentration of ozone in the boundary layer of the studyregion. Throughout the entire region (marine, coastal, and continental areas),higher concentrations were produced during the dry season (20–30 ppbv)than during the wet season (13–17 ppbv), likely due to the photochemicalproduction of ozone from biomass burning emissions. This seasonal variationobserved in the boundary layer contrasts with satellite data, that show highertotal tropospheric ozone columns during the wet season in the 0–15°Nregion; this means that the ozone annual cycles in the boundary layer and freetroposphere are out of phase.At the most pristine continental sites in the southern part of Venezuela,quite a `peculiar' diurnal variation was observed, with maximum concentrationsin the morning and a steady decrease of ∼0.6 ppbv hr-1 duringthe hours of high solar irradiation. Although dynamic aspects cannot be ruledout, the daytime ozone decrease, which cannot be explained by thewell-established `classical' continental O3 sinks, suggests thatin this region part of the ozone consumption is caused byHO x cycles at low NO x levels. Futurestudies to elucidate the causes of the daytime ozone decrease at thesecontinental sites should be undertaken.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 907-914 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of Cl2, CH4, and O2 were flash photolyzed at room temperature and pressures of ∽60-760 Torr to produce CH3O2. The CH3O2 radicals decay by the second-order process with k6 = (3.7 ± 0.3) × 10-13 cm3/sec in good agreement with other studies. This value ignores any removal by secondary radicals produced as a result of reaction (6), and therefore the true value might be as much as 30% lower. The value is independent of total pressure or the presence of H2O vapor. With SO2 also present, the CH3O2 decay becomes pseudo first order at sufficiently high SO2 pressure which indicates the reaction The value of (8.2 ± 0.5) × 10-15 cm3/sec at about 1 atm total pressure (mostly CH4) was found for CH3O2 removal by SO2, in good agreement with another recent measurement. This value can be equated with k1, unless the products rapidly remove another CH3O2 radical, in which case k1 would be a factor of 2 smaller.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 399-415 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of CFClCFCl and CF2CCl2 were studied at room temperature by chlorine- and oxygen-atom initiation. The chlorine-atom initiated oxidation of CFClCFCl yields CCl2FCF(O) as the exclusive product. Its quantum yield is ∼420, which gives k3a/k3b=210 where reactions (3a) and (3b) are The O(3P)—CFClCFCl reaction gives CClFO with a quantum yield of 0.80, polymer, and small amounts of an unidentified product which is probably cyclo-(CFCl)3. Thereaction paths are with k9a/k9=0.80. The overall reaction of O(3P) with CFClCFCl proceed one fifth as fast as the O(3P)-C2F4 reaction. When O2 is also present, the same free-radical chain oxidation occurs by O(3P)initiation as by chlorine-atom initiation.The chlorine-atom initiated oxidation of CF2CCl2 gives CF2ClCCl(O) as the major product, with quantum yields ranging from 42 to 85. Smaller amounts of CF2O and CCl2O are produced in equal amounts with quantum yields of ∼3.5. The reactions responsible for the products are The O(3P)-CF2CCl2interaction yields CF2O and with quantum yields of 1.0 and ∼0.85, respectively. In thepresence of O2 the radical chain products are observed, but the mechanism is different than that for other chloroolefins.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 589-604 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When Cl atoms react with CHClCHCl in the presence of O2 at 31°C, a long-chain oxidation occurs. The products are the geometrical isomer of the starting olefin and CHClO, HCl, CO, and CCl2O. The quantum yields of the oxygen-containing products are the same with both isomers and are Φ{CHClO} = 30, Φ{CO} = 11.7, and Φ{CCl2O} = 1.29. The chlorine atom adds to the olefin and is followed by O2 addition. The reaction then proceeds with k6a/k6b = 19 and k7a/k7 ∼ 0.5, where k7 ≡ k7a + k7b. The CCl2H radical oxidizes to regenerate the chain carrier.O(3P) reacts with CHClCHCl at 25°C with a rate coefficient of 6.6 × 108 M-1 sec-1 for trans-CHClCHCl and 2.8 × 108 M-1 sec-1 for cis-CHClCHCl. The reaction channels are with k1a/k1 = 0.23 and 0.28, respectively, for the cis and trans compounds. Reaction (1b) occurs 〈 4% of the time. Reaction (1c) leads to polymer production and presumably, via redissociation, to the geometrical isomer of the starting olefin. In the presence of O2 the same long-chain oxidation is observed as in the chlorine-atom initiated oxidation. The chain-initiating step is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CHCl + O}_{\rm 2} \to {\rm HO + ClCO} \to {\rm Cl + CO} $$\end{document}
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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