Ozone and its precursors over the United States: Sources, outflow, transpacific inflow, and hemispheric influence

This thesis examines the sources, outflow, and transpacific inflow of tropospheric ozone and its precursors in the United States using observations from two aircraft campaigns (ITCT-2K2, ICARTT) interpreted with a global three-dimensional chemical transport model (GEOS-Chem). We find a large springtime transpacific transport of Asian ozone plumes to the west coast of the United States in the free troposphere. Ozone production from the decomposition of peroxyacetylnitrate (PAN) during subsidence over the northeast Pacific represents a major and possibly dominant component of the ozone enhancement in these plumes. Strong dilution of Asian plumes, however, takes place during entrainment in the U.S. boundary layer, greatly reducing their impact at U.S. surface sites. California mountain sites are most sensitive to Asian pollution because of their exposure to the free troposphere. Extensive aircraft mapping of the U.S. boundary layer in summer confirms the recent decrease in nitrogen oxide (NOx) emissions required by recent regulation, and reveals a large overestimate of carbon monoxide (CO) emissions in current inventories. The model successfully simulates the export of anthropogenic NOx and its oxidation products, as well as the ozone-CO correlations in the U.S. boundary layer and its outflow, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export. However, the model greatly underestimates observed NOx in the upper troposphere, reflecting a higher-than-expected (factor of four) lightning source. This lightning source drives in turn a large ozone enhancement in the upper troposphere (>10 ppbv) with implications for radiative forcing and climate feedback through changes in lightning. Using the above constraints on ozone and its precursors we provide new estimates of North American anthropogenic, lightning, and biomass burning contributions to tropospheric ozone on the scale of the northern hemisphere.