Surface and lightning sources of nitrogen oxides over the United States: Magnitudes, chemical evolution, and outflow

We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3‐D model of tropospheric chemistry (GEOS‐Chem) to test current understanding of regional sources, chemical evolution, and export of NO x . The boundary layer NO x data provide top‐down verification of a 50% decrease in power plant and industry NO x emissions over the eastern United States between 1999 and 2004. Observed NO x concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NO x and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NO x observations with GEOS‐Chem requires a factor of 4 increase in modeled NO x yield per flash (to 500 mol/flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NO y ‐CO correlation analysis of the fraction f of North American NO x emissions vented to the free troposphere as NO y (sum of NO x and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO 3 but at higher altitudes is mostly PAN. The model successfully simulates NO y export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export.