With harmful ozone concentrations tied to meteorological conditions, EPA investigates the U.S. air quality implications of a changing climate. Consequently, the 03 NAAQS are most often exceeded during summertime hot spells in places with large natural or anthropogenic precursor emissions (e.g., cities and suburban areas). Table 2 The average maximum or minimum temperature and/or changes in their spatial distribution and duration, leading to a change in reaction rate coefficients and the solubility of gases in cloud water solution;The frequency and pattern of cloud cover, leading to a change in reaction rates and rates of conversion of S02to acid deposition;The frequency and intensity of stagnation episodes or a change in the mixing layer, leading to more or less mixing of polluted air with background air;Background boundary layer concentrations of water vapor, hydrocarbons, NOx, and 03, leading to more or less dilution of polluted air in the boundary layer and altering the chemical transformation rates;

Collisional removal of the v′=0 level of the A 2Σ+ state of the OH radical has been studied as a function of rotational level N′ at room temperature. OH in high rotational levels of the X 2Πi state were created by 193 nm photolysis of HNO3 and excited to A 2Σ+ by a tunable dye laser. Time decays of fluorescence at varying pressures were measured. For O2 and H2, the quenching cross section σQ decreased with increasing N′ until N′∼10; for higher N′ it appears to remain approximately constant. Xe behaves the same way except that the decrease continues to N′=15. For Kr, σQ appears to decrease to within experimental error of zero at N′=10; and for N2 it was within error of zero above N′=10. These results have implications for laser-induced fluorescence atmospheric monitoring of OH and combustion temperature determinations, as well as a fundamental understanding of collisional quenching. Quenching of OH, N′∼1, by HNO3 was found to be 81±8 Å2.

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The vapor-liquid equilibrium of organic species and water determines the partitioning of volatile organic species between the gas and aerosol phases in the atmosphere. Essential properties that govern this partitioning are the compounds' vapor pressures and the liquid-phase activity coefficients of the organic species. Key issues include (1) the amount of water absorbed by organic particles, both single-component and multicomponent, as a function of relative humidity and (2) how organic and water partitioning is altered as the relative humidity changes, for a fixed total (gas plus particle) quantity of each organic component. We present here calculations relating to each of these issues for organic molecules that are characteristic of those that have been identified in ambient aerosols. Uncertainties exist in knowledge of vapor pressures of atmospheric organics and in activity coefficients, which are calculated by the UNIFAC method. These uncertainties, the level of which is difficult to estimate because of a lack of appropriate thermodynamic data, can lead to significant uncertainty in predicted gas-aerosol partitioning. Current theories for estimating both vapor pressures and activity coefficients are likely to be improved eventually, but the methods discussed here will probably remain the procedures of choice for the immediate future.