Overnight Atmospheric Transport and Chemical Processing of Photochemically Aged Houston Urban and Petrochemical Industrial Plume

Overnight atmospheric transport and chemical evolution of photochemically aged Houston urban and petrochemical industrial plume were investigated in July 2005. We report here on the 26 July episode in which the aged plume was tagged 1.5 h before sunset with a pair of free-floating controlled meteorological balloons, which guided quasi-Lagrangian aircraft sampling in the plume as it was advected 300 km to the north over 8 h. The aged plume around sunset was well mixed within a 1600 m residual layer, and was characterized by enhanced levels of aerosol, O3, CO, olefins, acetaldehyde, total odd nitrogen compounds (NOy), and relatively small amounts (\u3c1 \u3eppbv) of NO x. The plume experienced appreciable shearing overnight due to the development of a low-altitude nocturnal jet between 300 and 500 m above mean sea level (MSL). However, the plume above 600 m MSL remained largely undiluted even after 8 h of transport due to lack of turbulent mixing above the jet. About 40-60% of the NOx present in the aged plume around sunset was found to be depleted over this 8 h period. A constrained plume modeling analysis of the quasi-Lagrangian aircraft observations suggested that by dawn this NO x was converted to nitric acid, organic nitrates, and peroxy acyl nitrates via reactions of NO3 radicals with enhanced levels of olefins and aldehydes in the plume. Sensitivity of NOx depletion to heterogeneous hydrolysis of N2O5 on aerosols was examined. These results have significant implications for the impacts of urban and industrial pollution on far downwind regions