Data gathered during the NASA GTE/CITE 2 airborne field campaign were analyzed and compared with diagnostically derived parameters to study the NOx photostationary state in the troposphere and the processes that control this photostationary state. Our analysis focussed on two sets of NO2/NO ratios derived from the data; these were based on overlapping NO and NO2 measurements made by two independent techniques; i.e., a chemiluminescent technique and a technique based on two-photon, laser-induced-fluorescence. While for any given 6- to 10-min time interval the two observed NO2/NO ratios often exhibited significant discrepancies, these discrepancies appeared to be mostly random rather than systematic, and as a result, the average difference for all time intervals with overlapping NOx measurements was only 12%. One notable exception, however, was the block of data gathered during the last three CITE 2 missions; during these three missions the ratios observed by the chemiluminescent technique were systematically larger than those observed by the laser-induced fluorescence technique by a factor of 1.6. When the data from these three missions were omitted from the analysis, the averages of the observed ratios agreed to within 1%. In contrast to a number of previous studies, the ratios predicted from photochemical model calculations were found to be reasonably consistent with the observed ratios, although on average they tended to fall about 20 – 25% below the observations. This agreement between observations and theory provides strong evidence in support of the importance of peroxy radicals in the fast photochemical cycling of NOx (and the concomitant photochemical production of O3) in both the marine and continental troposphere
