The Impact of Cloud Correction on the Redistribution of Reactive Nitrogen Species

Clouds are particularly important to air quality. Yet, correct prediction of clouds in time and space remains to be a great challenge for the air quality models. One aspect of cloud impact on air quality is the modification of photolysis reaction rates by clouds. Clouds can significantly alter the solar radiation in the wavelengths affecting the photolysis rates. Such modifications significantly impact atmospheric photochemistry and alter the chemical composition of the boundary layer. It also alters the partitioning of chemical compounds by creating a new equilibrium state. Since air quality models are often being used for air quality and emission reduction assessment, understanding the uncertainty caused by inaccurate cloud prediction is imperative. In this study we investigate the radiative impact of clouds in altering the partitioning of nitrogen species in the emission source regions. Such alterations affect the local nitrogen budget and thereby alter the atmospheric composition within the boundary layer. The results from two model simulations, one in which the model predicted clouds are used (control), and the other in which the satellite observed clouds have been assimilated in the model were analyzed. We use satellite retrieved cloud transmissivity, cloud top height, and observed cloud fraction to correct photolysis rates for cloud cover in the Community Multiscale Air Quality (CMAQ) modeling system. The simulations were performed at 4- and 12-km resolution domains over Texas, extending east to Mississippi, for the period of August 24 to August 31, 2000. The results clearly indicate that not using the cloud observations in the model can drastically alter the predicted atmospheric chemical composition within the boundary layer and exaggerate or under-predict the ozone concentrations. Cloud impact is acute and more pronounced over the emission source regions and can lead to drastic errors in the model predictions of ozone and its precursors. Clouds also increased the lifetime of ozone precursors leading to their transport out of the source regions and caused further ozone production downwind. The longer lifetimes for NOx and its transport over regions high in biogenic hydrocarbon emissions (in the eastern part of the domain) led to increased ozone production that was missing in the control simulation. An indirect impact of the clouds in the emission source areas is the alteration in partitioning of nitrogen oxides and the impact on nitrogen budget due to surface removal. This is caused by the disparity between the deposition velocity of NOx and the nitrates that are produced from oxidation of NOx. Under clear skies, NOx undergoes a chemical transformation and produces nitrates such as HNO3 and PAN. In the presence of thick clouds, due to the reduction in the photochemical activities, nitrogen monoxide (NO) rapidly consumes ozone (O3) and produces nitrogen dioxide (NO2) while the production of HNO3 and loss of NOx due to chemical transformation is reduced. Therefore, in one case there is more loss of nitrogen in the vicinity of emission sources. A detailed analysis of two emission source regions, Houston-Galveston and New Orleans area, will be presented. Acknowledgments. This work was accomplished under partial support from Cooperative Agreement between the University of Alabama in Huntsville and the Minerals Management Service on the Gulf of Mexico Issues.