Atmospheric heterogeneous stereochemistry.

While many biogenic and anthropogenic organic constituents in the atmosphere are surface-active and chiral, the role of stereochemistry in heterogeneous oxidation chemistry in the atmosphere has not yet been evaluated. Here, we present nonlinear vibrational surface spectra of fused silica substrates functionalized with quinuclidine diastereomers during exposure to 10(11) to 10(13) molecules of ozone per cm(3) in 1 atm helium to model ozone-limited and ozone-rich tropospheric conditions. Kinetic studies show that diastereomers that orient their reactive C=C double bonds toward the gas phase exhibit heterogeneous ozonolysis rate constants that are 2 times faster than diastereomers that orient their C=C double bonds away from the gas phase. Insofar as our laboratory model studies are representative of real world environments, our studies suggest that the propensity of aerosol particles coated with chiral semivolatile organic compounds to react with ozone may depend on stereochemistry. We expect that the differences in chemical accessibility will lead to the enrichment of one oxidation product stereoisomer over the other. The oxidation products could be gaseous or surface-bound, indicating that kinetic resolution could lead to the stereochemical enrichment of the gas phase or the aerosol, which may have also been important in prebiotic chemistry. Implications of these results for chiral markers that would allow for source appointments of anthropogenic versus biogenic carbon emissions are discussed.