Latitudinal distribution of reactive nitrogen in the free troposphere over the Pacific Ocean in late winter/early spring

Abstract

The late winter/early spring (February/March, 1994) measurements of Pacific Exploratory Mission‐West (PEM‐W) B have been analyzed to show latitudinal distributions (45°N to 10°S) of the mixing ratios of reactive nitrogen species (NO, peroxyacetylnitrate (PAN), HNO 3 , and NO y ), ozone, and chemical tracers (CO, NMHCs, acetone, and C 2 Cl 4 ) with a focus on the upper troposphere. Mixing ratios of all species are relatively low in the warm tropical and subtropical air south of the polar Jetstream (≈28°N) but increase sharply with latitude in the cold polar air north of the Jetstream. Noteworthy is the continuous increase in reservoir species (PAN and HNO 3 ) and the simultaneous decrease in NO x toward the northern midlatitudes. The Harvard global three‐dimensional model of tropospheric chemistry has been used to compare these observations with predictions. In the upper troposphere the magnitude and distribution of measured NO y and PAN as a function of latitude is well represented by this model, while NO x (measured NO + model calculated NO 2 ) is underpredicted, especially in the tropics. Unlike several previous studies, where model‐predicted HNO 3 exceeded observations by as much as a factor of 10, the present data/model comparison is improved to within a factor of 2. The predicted upper tropospheric HNO 3 is generally below or near measured values, and there is little need to invoke particle reactions as a means of removing or recycling HNO 3 . Comparison between measured NO y and the sum of its three main constituents (PAN + NO x + HNO 3 ) on average show a small mean shortfall (<15%). This shortfall could be attributed to the presence of known but unmeasured species (e.g., peroxynitric acid and alkyl nitrates) as well as to instrument errors.