Observational constraints for the source strengths, transport and partitioning of reactive nitrogen on regional and global scales

Reactive nitrogen (NOy) exerts control over the production of tropospheric ozone (O3) and the destruction of stratospheric O 3, plays an important role in the formation of secondary organic aerosol and represents a critical link between the atmosphere and biosphere. Accurate estimates of the spatial and temporal distribution of nitrogen oxide (NO x) emissions and their subsequent transport and chemical processing are critical to furthering our understanding of these processes. In this dissertation, several new approaches to understanding the role of nitrogen oxides in atmospheric chemistry are developed. Most of the observations and analyses presented are based on aircraft measurements used to describe and understand the distribution of NOx from the surface to the upper troposphere (UT) and to provide an understanding of the accuracy of satellite measurements.; First, new experiments to establish the absolute accuracy and long term precision of the standards maintained at the National Institute of Standards and Technology (NIST) are described. These standards serve as the references upon which calibration of the instruments used to make atmospheric measurements of O3, nitric oxide (NO) and nitrogen dioxide (NO2) are based. Gas-phase titration of ozone with nitric oxide was used to show that the O3, NO and NO2 standards are self-consistent to within 1%. Prior experiments had only established these three to be self-consistent to 4%. Following this, the implementation of the Thermal Dissociation - Laser Induced Fluorescence (TD-LIF) Technique for measurements of NO2, total peroxy nitrates (SigmaPNs), total alkyl nitrates (SigmaANs) and nitric acid (HNO3) from an aircraft platform is discussed and the measurements obtained are compared directly to analogous measurements made aboard the same aircraft or different aircraft during in-flight comparisons.; Detailed observations of the partitioning of reactive nitrogen in the upper troposphere, during a period of intense convective activity, are used to provide new and unique constraints on the chemistry occurring downwind of convection and the rate at which air in the UT is recycled, previously only the province of model analyses. These direct measures of atmospheric rates present a challenge to our thinking about the processes governing UT O3 and its impact on climate. These measurements along with ones from periods without active convection are used to discuss the partitioning of NOy over the remote pacific during spring and over Continental North America during summer. The observations over the remote pacific reveal a strong role for SigmaPNs in the NOy budget and confirm earlier analyses and model predictions showing that the thermal dissociation of SigmaPNs is a significant NOx source to the remote Pacific. In contrast the vertical distribution and partitioning of reactive nitrogen over the North American continent during summer suggests a strong role for lightning initiated NOx production. Comparison to satellite observations during these experiments provides support for the accuracy of the satellite measurements. Finally, the utility of satellite measurements, which were examined in comparison to the aircraft measurements of NO2, to observe the spatial and temporal distribution of NOx emissions from fertilized agricultural soils is shown.{09}These results demonstrate that satellite observations of NO 2 capture the short intense NOx pulses following fertilizer application and subsequent precipitation, and illustrate the strong potential for the use of satellite observations of NO2 in constraining NO x emissions sources.