Kinetic studies of the photochemistry of the urban troposphere

Abstract A mathematical description of the photochemical processes of the troposphere, which incorporates chemical kinetics, time-varying sources of trace contaminants, solar flux variations, bulk air flow, and a geographical matrix of “reaction volumes”, has been formulated with the primary aim of studying the fundamental chemistry of the troposphere. To this end, the chemical set utilizes 143 reactions in 76 species which include extensive O-H-N, hydrocarbon, and sulfur subsets, as well as an assessment of aerosol interactions. Comparison of calculations for Hudson County, NJ with atmospheric diurnal patterns and concentration data show agreement to the order of a factor of two for the following species: NO, NO2, O3, SO2, HCHO, CH3CHO, HNO2, HNO3, acrolein, and PAN. The interplay among NO, NO2, and O3 provides the principal driving force for the photochemistry; the balance among these species is determined by interactions with organic and inorganic radicals. The species active in oxidizing NO to NO2 are shown to be (in order of importance) O3, RȮ2, HȮ2, and NȮ3. Olefin attack occurs principally by HȮ (daytime) or O3 (nighttime). The following peak values of important reactive intermediates are predicted: HȮ2, 3 × 10−5 ppm; CH3Ȯ2, 9 × 10−7ppm; HȮ, 7 × 10−8 ppm; O, 3 × 10−9 ppm.

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