Reactive nitrogen compounds in the troposphere: Observations, transport, and photochemistry

Oxides of nitrogen critically control the photochemical production of ozone and account for approximately 1/3 of the total acid deposition in North America. This dissertation presents the results of three studies designed to enhance our knowledge of the distribution, transport, and photochemistry of reactive (or odd) nitrogen compounds in the troposphere.;Concentrations of odd nitrogen were measured in both urban and rural air advected from the polluted east coast of North America to the western Atlantic ocean as part of the 1986 Western ATlantic Ocean eXperiment. On January 9, 1986, median (NOy) rose from 0.28 ppbv in the free troposphere (FT) to 1.38 ppbv in the marine boundary layer (MBL), and ratios of peroxyacetyl nitrate (PAN) to NOy were similar to those observed at a non-urban site in Colorado during autumn. The maximum gross flux of nitrogen through the FT and MBL between 31.5-44.1;Reactive nitrogen compounds, carbon monoxide, and ozone were measured over the central United States in 1985 and 1986 from a twin-jet aircraft. Vertical profiles of reactive nitrogen compounds show dramatic perturbations due to the effects of violent convective activity. Measurements made in stable air dominated by high pressure contrast with those made near organized, isolated convective cells, which efficiently transport odd nitrogen to the upper troposphere. The layered lifting associated with episodes of cold frontal passage efficiently mixes both the upper and middle troposphere, however. Rapid injection of boundary layer air into the upper troposphere, where colder temperatures and higher wind velocities combine to extend both the lifetimes and range of influence of a variety of primary and secondary pollutants, will increase the rate of photochemical ozone production aloft and may thus exacerbate the greenhouse effect.;Finally, the photolysis rate coefficients (j) of several alkyl nitrates (RONO...