Troposphere amines

Tuazon et al. (1984a) investigated the atmospheric reactions of TV-nitrosodimethylamine and dimethylnitramine in an environmental chamber utilizing in situ long-path Fourier transform infared spectroscopy. They irradiated an ozone-rich atmosphere containing A-nitrosodimethyl-amine. Photolysis products identified include dimethylnitramine, nitromethane, formaldehyde, carbon monoxide, nitrogen dioxide, nitrogen pentoxide, and nitric acid. The rate constants for the reaction of fV-nitrosodimethylamine with OH radicals and ozone relative to methyl ether were 3.0 X 10 and <1 x 10 ° cmVmolecule-sec, respectively. The estimated atmospheric half-life of A-nitrosodimethylamine in the troposphere is approximately 5 min. 

The ozone concentration in the troposphere during the daytime is typically about 1 pphm (parts per hundred million parts of air by volume) [20], Values up to 100 pphm were measured in some photochemical smog areas. The molecular mechanism of the ozone aging of diene based elastomers was studied in detail and is well understood [19,21], Products or intermediates different from those arising in autoxidation or photo-oxidation of polymers were identified ozonides (3), zwitterions (4), diperoxides (5), polyperoxides (6), polymeric ozonides (7) and terminal aldehydes (8). Reactivity of aminic antiozonants (AOZ) with these species accounts for the protection of rubbers against atmospheric 03. AOZ must also possess antioxidant properties, because the free radical processes are concerted with ozonation due to the permanent presence of oxygen. 

The photolysis rate of atmospheric NO2 has been measured, and its dependences upon parameters such as the solar zenith angle and the amount of cloud cover have been evaluated.The photochemistry of small molecules containing sulphur, and its implications for the atmospheric S cycle have been discussed, as has the role of stratospheric reactive nitrogen as a source for species such as NO and HNO3 in the unpolluted troposphere. Ammonia concentrations have been calculated in the atmospheres of both Earth and Saturn the far-u.v. photolysis of mixtures of NH3 with methane results in the formation of amines and nitriles, and the relevance of these results to the evolution of primitive atmospheres has been discussed. ... 

Fig. 2.26 The biogeochemical nitrogen cycle. A ammonia synthesis (man-made N fixation), B oxidation of ammonia (indnstrial prodnction of nitric acid), C fertilizer application, D formation of NO due to high-temperature processes, E Oxidation of N2O within the stratosphere, F oxidation of NO within the troposphere, G ammonia deposition and transformation into ammonium, H biogenic emission, I biogenic N fixation, K denitrification, L nitrification, M assimilation (biogenic formation of amino adds), N mineralization. RNH2 organic bonded N (e. g. amines).

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