Reactive nitrogen distribution and partitioning in the North American troposphere and lowermost stratosphere

A comprehensive group of reactive nitrogen species (NO, NO2, HNO3, HO2NO2, PANs, alkyl nitrates, and aerosol-NOÀ) were measured over North America during 3 July/August 2004 from the NASA DC-8 platform (0.1–12 km). Nitrogen containing tracers of biomass combustion (HCN and CH3CN) were also measured along with a host of other gaseous (CO, VOC, OVOC, halocarbon) and aerosol tracers. Clean background air as well as air with influences from biogenic emissions, anthropogenic pollution, biomass combustion, convection, lightning, and the stratosphere was sampled over the continental United States, the Atlantic, and the Pacific. The North American upper troposphere (UT) was found to be greatly influenced by both lightning NOx and surface pollution lofted via convection and contained elevated concentrations of PAN, ozone, hydrocarbons, and NOx. Observational data suggest that lightning was a far greater contributor to NOx in the UT than previously believed. PAN provided a dominant reservoir of reactive nitrogen in the UT while nitric acid dominated in the lower troposphere (LT). Peroxynitric acid (HO2NO2) was present in sizable concentrations peaking at around 8 km. Aerosol nitrate appeared to be mostly contained in large soil based particles in the LT. Plumes from Alaskan fires contained large amounts of PAN and aerosol nitrate but little enhancement in ozone. A comparison of observed data with simulations from four 3-D models shows significant differences between observations and models as well as among models. We investigate the partitioning and interplay of the reactive nitrogen species within characteristic air masses and further examine their role in ozone formation.