Abstract

The nocturnal nitrogen oxides, NO3 and N2O5, are important to the chemical transformation and transport of NOx, O3 and VOC. Their concentrations, sources and sinks are known to be vertically stratified in the nighttime atmosphere. In this paper, we report vertical profiles for NO3 and N2O5 measured from an aircraft (the NOAA P‐3) as part of the New England Air Quality Study in July and August 2004. The aircraft data are compared to surface measurements made in situ from a ship and by long‐path DOAS. Consistent with previous, vertically resolved studies of NO3 and N2O5, the aircraft measurements show that these species occur at larger concentrations and are longer lived aloft than they are at the surface. The array of in situ measurements available on the P‐3 allows for investigation of the mechanisms that give rise to the observed vertical gradients. Selected vertical profiles from this campaign illustrate the role of biogenic VOC, particularly isoprene and dimethyl sulfide, both within and above the nocturnal and/or marine boundary layer. Gradients in relative humidity and aerosol surface may also create a vertical gradient in the rate of N2O5 hydrolysis. Low‐altitude intercepts of power plant plumes showed strong vertical stratification, with plume depths of 80 m. The efficiency of N2O5 hydrolysis within these plumes was an important factor determining the low‐level NOx and O3 transport or loss at night. Averages of nocturnal O3, NO2, NO3 and N2O5 binned according to altitude were consistent with the trends from individual profiles. While production rates of NO3 peaked near the surface, lifetimes of NO3 and N2O5 were maximum aloft, particularly in the free troposphere. Variability in NO3 and N2O5 was large and exceeded that of NO2 or O3 because of inhomogeneous distribution of NOx emissions and NO3 and N2O5 sinks.

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