Estimation of activation energies for nitrous oxide, carbon dioxide, nitrogen dioxide, nitric oxide, oxygen, and nitrogen reactions by a bond-energy method

1969 ◽  
Vol 73 (11) ◽  
pp. 3941-3946 ◽  
Author(s):  
S. E. Mayer

2005 ◽  
Vol 9 (23) ◽  
pp. 1-28 ◽  
Author(s):  
Michael Keller ◽  
Ruth Varner ◽  
Jadson D. Dias ◽  
Hudson Silva ◽  
Patrick Crill ◽  
...  

Abstract Selective logging is an extensive land use in the Brazilian Amazon region. The soil–atmosphere fluxes of nitrous oxide (N2O), nitric oxide (NO), methane (CH4), and carbon dioxide (CO2) are studied on two soil types (clay Oxisol and sandy loam Ultisol) over two years (2000–01) in both undisturbed forest and forest recently logged using reduced impact forest management in the Tapajos National Forest, near Santarem, Para, Brazil. In undisturbed forest, annual soil–atmosphere fluxes of N2O (mean ± standard error) were 7.9 ± 0.7 and 7.0 ± 0.6 ng N cm−2 h−1 for the Oxisol and 1.7 ± 0.1 and 1.6 ± 0.3 ng N cm−2 h−1 for the Ultisol for 2000 and 2001, respectively. The annual fluxes of NO from undisturbed forest soil in 2001 were 9.0 ± 2.8 ng N cm−2 h−1 for the Oxisol and 8.8 ± 5.0 ng N cm−2 h−1 for the Ultisol. Consumption of CH4 from the atmosphere dominated over production on undisturbed forest soils. Fluxes averaged −0.3 ± 0.2 and −0.1 ± 0.9 mg CH4 m−2 day−1 on the Oxisol and −1.0 ± 0.2 and −0.9 ± 0.3 mg CH4 m−2 day−1 on the Ultisol for years 2000 and 2001. For CO2 in 2001, the annual fluxes averaged 3.6 ± 0.4 μmol m−2 s−1 on the Oxisol and 4.9 ± 1.1 μmol m−2 s−1 on the Ultisol. We measured fluxes over one year each from two recently logged forests on the Oxisol in 2000 and on the Ultisol in 2001. Sampling in logged areas was stratified from greatest to least ground disturbance covering log decks, skid trails, tree-fall gaps, and forest matrix. Areas of strong soil compaction, especially the skid trails and logging decks, were prone to significantly greater emissions of N2O, NO, and especially CH4. In the case of CH4, estimated annual emissions from decks reached extremely high rates of 531 ± 419 and 98 ± 41 mg CH4 m−2 day−1, for Oxisol and Ultisol sites, respectively, comparable to wetland emissions in the region. We calculated excess fluxes from logged areas by subtraction of a background forest matrix or undisturbed forest flux and adjusted these fluxes for the proportional area of ground disturbance. Our calculations suggest that selective logging increases emissions of N2O and NO from 30% to 350% depending upon conditions. While undisturbed forest was a CH4 sink, logged forest tended to emit methane at moderate rates. Soil–atmosphere CO2 fluxes were only slightly affected by logging. The regional effects of logging cannot be simply extrapolated based upon one site. We studied sites where reduced impact harvest management was used while in typical conventional logging ground damage is twice as great. Even so, our results indicate that for N2O, NO, and CH4, logging disturbance may be as important for regional budgets of these gases as other extensive land-use changes in the Amazon such as the conversion of forest to cattle pasture.



1983 ◽  
Vol 61 (12) ◽  
pp. 2767-2772 ◽  
Author(s):  
Robert Anderson Ross ◽  
Craig Fairbridge

Reactions of 1-butene with nitric oxide from 623 to 723 K and with oxygen from 433 to 573 K have been studied in a differential flow system over manganese(III) oxide. Nitrous oxide was formed in the reaction of the hydrocarbon with nitric oxide along with products of complete combustion. The apparent activation energies were respectively 69 ± 4, 78 ± 4, and 30 ± 4 kJ mol−1 for nitrogen, carbon dioxide, and nitrous oxide reaction rates. The corresponding pre-exponential factors were 1.72 × 10−1 and 1.16 mol0.5 L−0.5 m2 g−1, and 1.99 × 10−2 mol−0.35 L0.35 m2 g−1. In the reaction with oxygen, apparent activation energies of 183 ± 4, 523 to 503 K, and 88 ± 4 kJ mol−1, 503 to 433 K, were determined with pre-exponential factors 1.74 × 1015 and 2.94 × 105 mol0.3 m−2 g−1. During catalysis the oxide underwent a partial phase change from α to γ in both reactions. Additionally, nitrate species were present on the surface after oxidation with nitric oxide. Kinetic expressions have been derived and mechanisms proposed for both reactions which may occur in emission control systems requiring the removal of NOx and unburned hydrocarbons.



1978 ◽  
Vol 56 (23) ◽  
pp. 2934-2939 ◽  
Author(s):  
D. L. Singleton ◽  
R. J. Cvetanović

Rate constants for the reactions O(3P) + HX → OH + X (X = Br, I) have been determined by a phase shift technique. Oxygen atoms were generated by modulated mercury photosensitized decomposition of nitrous oxide, and were monitored by the chemiluminescence from the reaction with nitric oxide. Over the temperature interval 298–554 K, the rate constants are satisfactorily represented by the Arrhenius expressions kO+HBr = (8.09 ± 0.86) × 109 exp (−3.59 ± 0.08)/RT and kO+HI = (2.82 ± 0.27) × 1010 exp (−1.99 ± 0.07)/RT, where the units are ℓ mol−1 s−1 and kcal mol−1. The indicated uncertainties are one standard deviation. The results of bond energy–bond order calculations, incorporating recently proposed modifications, are discussed.



1969 ◽  
Vol 14 (2) ◽  
pp. 181-189 ◽  
Author(s):  
H.Edward Mishmash ◽  
Clifton E. Meloan


1955 ◽  
Vol 33 (5) ◽  
pp. 843-848
Author(s):  
T. M. Rohr ◽  
W. Albert Noyes Jr.

The addition of ethane to nitrogen dioxide either during exposure to radiation transmitted by pyrex, or afterwards, reduces the amount of oxygen formed. At room temperature this is apparently due to the effectiveness of ethane in promoting the reverse reaction of nitric oxide and oxygen to form nitrogen dioxide. At temperatures over 100° there is a reaction which uses oxygen atoms produced in the primary process. Nitroethane (or nitrosoethane) is formed along with carbon monoxide, carbon dioxide, and some methane. The results suggest that acetaldehyde is an intermediate, but acetaldehyde could not be detected because it would react thermally with nitrogen dioxide. It is not possible to give a complete explanation of the results, but suggestions can be made which might form the basis for later work.





Plants ◽  
2019 ◽  
Vol 8 (12) ◽  
pp. 587 ◽  
Author(s):  
Dilantha Gunawardana

Azolla is a genus of aquatic ferns that engages in a unique symbiosis with a cyanobiont that is resistant to cultivation. Azolla spp. are earmarked as a possible candidate to mitigate greenhouse gases, in particular, carbon dioxide. That opinion is underlined here in this paper to show the broader impact of Azolla spp. on greenhouse gas mitigation by revealing the enzyme catalogue in the Nostoc cyanobiont to be a poor contributor to climate change. First, regarding carbon assimilation, it was inferred that the carboxylation activity of the Rubisco enzyme of Azolla plants is able to quench carbon dioxide on par with other C3 plants and fellow aquatic free-floating macrophytes, with the cyanobiont contributing on average ~18% of the carboxylation load. Additionally, the author demonstrates here, using bioinformatics and past literature, that the Nostoc cyanobiont of Azolla does not contain nitric oxide reductase, a key enzyme that emanates nitrous oxide. In fact, all Nostoc species, both symbiotic and nonsymbiotic, are deficient in nitric oxide reductases. Furthermore, the Azolla cyanobiont is negative for methanogenic enzymes that use coenzyme conjugates to emit methane. With the absence of nitrous oxide and methane release, and the potential ability to convert ambient nitrous oxide into nitrogen gas, it is safe to say that the Azolla cyanobiont has a myriad of features that are poor contributors to climate change, which on top of carbon dioxide quenching by the Calvin cycle in Azolla plants, makes it an efficient holistic candidate to be developed as a force for climate change mitigation, especially in irrigated urea-fed rice fields. The author also shows that Nostoc cyanobionts are theoretically capable of Nod factor synthesis, similar to Rhizobia and some Frankia species, which is a new horizon to explore in the future.



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