Nitrogen dioxide, tropospheric

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. 

Photolytic. Irradiation of vinyl chloride in the presence of nitrogen dioxide for 160 min produced formic acid, HCl, carbon monoxide, formaldehyde, ozone, and trace amounts of formyl chloride and nitric acid. In the presence of ozone, however, vinyl chloride photooxidized to carbon monoxide, formaldehyde, formic acid, and small amounts of HCl (Gay et al, 1976). Reported photooxidation products in the troposphere include hydrogen chloride and/or formyl chloride (U.S. EPA, 1985). In the presence of moisture, formyl chloride will decompose to carbon monoxide and HCl (Morrison and Boyd, 1971). Vinyl chloride reacts rapidly with OH radicals in the atmosphere. Based on a reaction rate of 6.6 x lO" cmVmolecule-sec, the estimated half-life for this reaction at 299 K is 1.5 d (Perry et al., 1977). Vinyl chloride reacts also with ozone and NO3 in the gas-phase. Sanhueza et al. (1976) reported a rate constant of 6.5 x 10 cmVmolecule-sec for the reaction with OH radicals in air at 295 K. Atkinson et al. (1988) reported a rate constant of 4.45 X 10cmVmolecule-sec for the reaction with NO3 radicals in air at 298 K. 

Noxon, J. F., Nitrogen Dioxide in the Stratosphere and Troposphere Measured by Ground-Based Absorption Spectroscopy, Science, 189, 547-549 (1975). 

The evolution of the emissions of some atmospheric pollutants in Europe (EU-15) in the period 1990-1999 has been presented in the report of Goodwin and Mareckova (2002). The report includes acidifying pollutants (ammonia, sulfur dioxide, and nitrogen oxides), tropospheric ozone precursors, NMVOCs, carbon monoxide, and particulate matter... 

Nitrogen dioxide is about 20 to 50% of the total nitrogen oxides NO, (NO, NOz, HN03, N2Os), while CIO represents about 10 to 15% of the total chlorine species CIO, (Cl, CIO, HCI) at 25 to 30 km. Hence, the rate of ozone removal by CIO, is about equal to that by NO, if the amounts of NO, are equal to those of CIO,. According to a calculation by Turco and Whitten (981), the reduction of ozone in the stratosphere in the year 2022 with a continuous use of chlorofluoromethanes at present levels would be 7%. Rowland and Molina (843) conclude that the ozone depletion level at present is about 1%, but it would increase up to 15 to 20% ifthechlorofluoromethane injection were to continue indefinitely at the present rates. Even if release of chlorofluorocarbons were stopped after a large reduction of ozone were found, it would take 100 or more years for full recovery, since diffusion of chlorofluorocarbons to the stratosphere from the troposphere is a slow process. The only loss mechanism of chlorofluorocarbons is the photolysis in the stratosphere, production of HCI, diffusion back to the troposphere, and rainout. 

Molecular oxygen photodissociation is feeding reaction (1) with atomic oxygen in the stratosphere, the part of the atmosphere extending from above the troposphere to about 50 km. In the troposphere, the lowest part of the atmosphere extended up to 7-16 km, 02 photolysis is not significant. Nitrogen dioxide (N02) photolysis provides the required 03P for 03 production ... 

Ozone forms in the upper stratosphere from molecular oxygen under the influence of UV solar radiation. In the lower stratosphere and troposphere, the source of ozone is the decomposition of nitrogen dioxide under the influence of UV and visible radiation. The formation of the vertical profile of ozone concentration is connected with its meridional and vertical transport. The general characteristic of this profile is the total amount of ozone measured by the thickness of its layer given in Dobson units (1 DU = 0.001 cm). 

Only a small percentage of the chlorine released by photolysis of CFCs is present in the active forms as Cl or CIO, however. Most of it is bound up in reservoir compounds such as hydrogen chloride and chlorine nitrate, formed respectively by hydrogen abstraction (equation 10) from methane and addition (equation 11) to nitrogen dioxide. Slow transport of these reservoir species across the tropopause, followed by dissolution in tropospheric water and subsequent rain-out, provide sink processes for stratospheric chlorine. 

Nitrogen dioxide is the most important photochemically active component of the troposphere, ft absorbs not only in UV but also in the visible range (Figure 9.6), so it is able to undergo photochemical reactions within the whole atmosphere. 

The tropospheric nitric oxide is produced from molecular nitrogen or its compounds during high temperature combustion processes thus it is mostly of anthropogenic origin. Nitrogen dioxide is produced by further oxidation of NO from these compounds other nitrogenous species are formed. 

Photochemical production of ozone in the troposphere occurs from the photolysis of nitrogen dioxide (N02) during the daytime, producing oxygen atoms (O) ... 

Nitrogen dioxide photolysis is a key driver of tropospheric atmospheric chemistry since it leads directly to the production and eventual consumption of ozone during the daytime as follows ... 

The temperature and density structure of the troposphere, along with the concentrations of major constituents, are well documented and altitude profiles have been measured over a wide range of seasons and latitudes for the minor species water, carbon dioxide, and ozone. A few profiles are available for carbon monoxide, nitrous oxide, methane, and molecular hydrogen, while only surface or low-altitude measurements have been made for nitric oxide, nitrogen dioxide, ammonia, sulfur dioxide, hydrogen sulfide, and nonmethane hydrocarbons. No direct measurements of nitric acid and formaldehyde are available, though indirect information does exist. The concentrations of a number of other important species, such as peroxides and oxy and peroxy radicals, have never been determined. Therefore, while considerable information concerning trace constituent concentrations is available, the picture is far from complete. 

The oxidation of nitric oxide in small concentrations in the troposphere by dioxygen is very slow. As shown in Scheme 21, nitric oxide is oxidized to nitrogen dioxide (ti/2 several days) either by HOO- radicals or by ozone. Reaction of nitrogen dioxide with hydroxide radicals forms nitric acid (ti/2 several days). Rain washes nitric acid out, thus acidic rain is formed. 

In addition to being a key player in the CO and CH4 oxidation chains leading to the chemical production of O3 in the troposphere, NO also leads to the chemical production of HNO3, the fastest growing component of acidic precipitation. NO is chemically transformed to nitrogen dioxide (NO2) and then to NO via the following reactions ... 

Compare and contrast the roles of ozone (O3) and nitrogen dioxide (NO2) in the stratosphere and in the troposphere. 

Thus the net effect of dissociating nitrogen dioxide is neutral. Net production of tropospheric ozone occurs as a result of other reactions that convert NO into NO2 without destroying ozone. There are many such reactions, most of which involve the photooxidation of chemicals like carbon monoxide, methane and other hydrocarbons. Since these are produced by traffic and industrial processes, ozone production is a feature of polluted regions, and ozone itself is considered a pollutant at low levels of the atmosphere where it is detrimental to human and other life forms. Sinks of ozone include photodissociation and reactions with OH and HO2 (as in the stratosphere) and deposition. 

In the visible region, the absorption by nitrogen dioxide can also contribute to the optical depth, especially in the lower stratosphere and troposphere. Moreover, molecular oxygen has two weak bands in the red region of the solar spectrum near 0.7 gm. 

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