Kinetics of NOx in the upper troposphere: new constraints on satellite remote sensing of lightning NOx

Satellite retrievals of NO2, O3, and HNO3 have been used in conjunction with chemical transport models, such as GEOS-Chem, to constrain the amount of NOx emitted annually from lightning by comparing the model to both observed NO2 column densities and to upper tropospheric (UT) concentrations of O3 and HNO3. Recent experiments have provided evidence for two changes to the kinetics of NOx in the UT. First, CH3O2NO2 has been shown to be an important temporary sink for NOx, suppressing NOx in the UT. Second, the rate coefficient for the reaction of OH with NO2 at the temperatures and pressures of the UT is slower than in current recommendations. We investigate the impact of updated kinetics that are consistent with in situ observations on model predictions of NO2, O3, and HNO3 concentrations and columns and on the inferred constraints on lightning NOx emissions. Changes to NO2, O3, and HNO3 concentrations resulting from the new kinetics are above the level of uncertainty in daily satellite observations. We hypothesize that the new kinetics will require an increase in lightning NOx emissions to match models to observations, and are working to confirm and quantify this increase.