Nitrogen Oxide Cycles

FIGURE 7 Compounds participating in the tropospheric nitrogen oxides cycle and their interrelations. [From Warneck, R (1999). Chemistry of the Natural Atmosphere, Academic Press, San Diego.]... 

The final products are then sulphuric acid, nitrogen oxide and oxygen the two latter react and the cycle goes on. Theoretically therefore, the nitrous fumes are never used up. In practice, however, some slight replacement is needed and this is achieved by adding a little concentrated nitric acid to the mixture in the Glover tower ... 

Table 19-1 demonstrates that with the exception of water vapor, all of these cycles have been severely perturbed by human activity. Of course, all of these cycles are also linked in many ways. For example, the combustion of fossil fuel has increased the fluxes of carbon, sulfur, and nitrogen oxides to the atmosphere. Denitrification, the production of N2O, is linked with the production of CO2 during respiration and decay. And of course, other important cycles are involved which are not depicted here. Look back at Fig. 17-8, which sums up the climate forcings by the key agents. 

The extent of formation of these NOC depends upon the presence of nitrogen oxides present in the atmosphere during the manufacturing cycle. The major contaminants are NDMA, A-nitrosodiethylamine (NDEA), A-nitrosopyrrolidine (NPYR), NMOR, A-nitrosodiphenylamine (NDPhA), A-nitrosopiperidine (NPIP) and A-nitrosodibutylamine (NDBA)68. NMOR was found in the hot process areas NDMA occurred in tube production areas in which NDPhA was being used as retarder and tetramethylthiuram disulphide as an accelerator. Figure 12 shows a proposed reaction scheme of formation of NOC in the rubber industry and subsequent exposure67. 

There were two important innovations in the development of these oxidative cycles the use of carbon monoxide which had previously been considered a relatively inert molecule in the atmosphere to regenerate the hydroperoxy radical via Reactions 2-6 and 2-7 and the use of peroxy radicals HO, and RO, to oxidize nitric oxide to nitrogen dioxide. 

The study of the biosynthesis of inorganic nitrogen oxides has a long and distinguished history, principally in the field of microbial and plant nitrogen metabolism (Zumft, 1993). Relatively recently, it has been found that NO, in addition to other species such as nitrite, nitrate, and NjO, is a true intermediate in the biological nitrogen cycle, as described in detail in Chapter 9. 

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