Fraction and composition of NOy transported in air masses lofted from the North American continental boundary layer

Abstract

Five field studies have included research aircraft flights over the continental United States and the western North Atlantic Ocean from 1996 through 2000 in spring, summer, and fall seasons. The major source of NOx in this region is fossil fuel combustion, which is localized within the continental boundary layer (CBL). We use CO as a tracer of these anthropogenic emissions to estimate the fraction of the emitted NOx that is exported to the free troposphere (FT), either as NOx itself or as its oxidation products. This export was identified as plumes enhanced in CO above an estimated background by at least 30 ppbv, which account for 20–31% of the air parcels sampled in the FT during the five field studies. These plumes were encountered throughout the FT up to the 8 km ceiling of the aircraft but were primarily located just above the CBL with average altitudes of 3.0–4.1 km above ground level. In the summer over the continent, only 20 ± 5% of the originally emitted nitrogen oxides was transported in those plumes. This fraction is in reasonable accord with model results, but the models include only deep convection and not the shallow CBL venting mechanisms responsible for the observed plumes. During the two field studies in the early fall and in the spring over the western North Atlantic, we find that 9 ± 4% of the NOy was transported, although Li et al. [2004] suggest that this is an underestimate and that 15 ± 11% is more accurate. Both of these numbers indicate that model results in the literature overestimate the amount of NOy transported from the CBL to the FT. In these five field studies, HNO3 generally accounted for one‐half to two‐thirds of the NOy, which is in contrast to the dominance by NOx and organic nitrates suggested by models. Over the North Atlantic, this difference is likely due to further photochemical processing of the NOy species within the FT and over the continent due to the different transport mechanism considered in the models.