Heterogeneous N₂O₅ chemistry in the Houston atmosphere

Heterogeneous reactions have the potential to significantly impact urban ozone formation and total reactivity of the atmosphere. This dissertation used comparisons between photochemical modeling predictions and field measurements to examine heterogeneous N₂O₅ chemistry in Southeast Texas. Heterogeneous reactions of N₂O₅ can lead to two different products: nitric acid (HNO₃) and nitryl chloride (ClNO₂). The formation of HNO₃ results in a loss of reactive nitrogen from the atmosphere. In contrast ClNO₂ photolysis forms Cl radicals and NO₂, both of which promote ozone formation in the troposphere. Preliminary modeling identified key uncertainties and the need to perform more refined modeling which included updated PM emissions estimates, an updated gas-phase N₂O₅ hydrolysis reaction rate constant, updated reactive uptake coefficients, and the inclusion of ClNO₂ as a product of heterogeneous N₂O₅ uptake. Refined modeling which incorporated all of these improvements was carried out and was the first comprehensive modeling of this chemistry performed for an urban air pollution episode. Comparisons of aerosol surface area concentrations, N₂O₅ concentrations, HNO₃ concentrations, and ClNO₂ concentrations with ambient data showed that model predictions were reasonable. The exceptions to this were 1) over-predictions of aerosol surface area concentration peaks at altitudes above 1500 meters and 2) over-prediction of N₂O₅ concentrations in the Houston Ship Channel. Further analysis is needed to identify the reasons for these over-predictions. Other key findings from this modeling include the model prediction of inland chlorine concentrations high enough to form ClNO₂ and the prediction that a large portion of atmospheric chlorine is cycled through ClNO₂, therefore making the inclusion of ClNO₂ into photochemical models essential for properly simulating chlorine chemistry. In addition, modeling suggested that the chemistry leads to significant increases of NO[subscript x] at night, but decreases in daytime NO[subscript x] concentrations and that the overall effect was to decrease ozone concentrations. Further investigation into the effect of ClNO₂ as a chlorine source showed that likely ozone increases in the Houston area caused by the presence of this compound are on the order of several ppb. Further analyses showed that vertical dispersion and local atmospheric composition moderated the effect of nitryl chloride on ozone mixing ratios.