ALBERT

Description: In-situ observations of tropospheric HO(x) (OH and HO2) obtained during four NASA airborne campaigns (SUCCESS, SONEX, PEM-Tropics B and TRACE-P) are reevaluated using the NASA Langley time-dependent photochemical box model. Special attention is given to previously diagnosed discrepancies between observed and predicted HO2 which increase with higher NO(x) levels and at high solar zenith angles. This analysis shows that much of the model discrepancy at high NO(x) during SUCCESS can be attributed to modeling observations at time-scales too long to capture the nonlinearity of HO(x) chemistry under highly variable conditions for NO(x). Discrepancies at high NO(x) during SONEX can be moderated to a large extent by complete use of all available precursor observations. Differences in kinetic rate coefficients and photolysis frequencies available for previous studies versus current recommendations also explain some of the disparity. Each of these causes is shown to exert greater influence with increasing NO(x) due to both the chemical nonlinearity between HO(x) and NO(x) and the increased sensitivity of HO(x) to changes in sources at high NO(x). In contrast, discrepancies at high solar zenith angles will persist until an adequate nighttime source of HO(x) can be identified. It is important to note that this analysis falls short of fully eliminating the issue of discrepancies between observed and predicted HO(x) for high NO(x) environments. These discrepancies are not resolved with the above causes in other data sets from ground-based field studies. Nevertheless, these results highlight important considerations in the application of box models to observationally based predictions of HO(x) radicals.