Laboratory measurements of the heterogeneous oxidation of condensed-phase organic molecular makers for meat cooking emissions

Multiphase oxidation of trace organic constituents inside of complex atmospheric particles is not well understood. In this study, organic aerosol formed from flash-vaporized residual grease from meat cooking was exposed to atmospherically relevant ozone concentrations in a smog chamber for 4-6 h. Changes in particle composition were measured to determine reaction rates for important molecular markers used for source apportionment analysis (oleic acid, palmitoleic acid, and cholesterol). Results are also presented for palmitic and stearic acids and likely reaction products. To quantify oxidation rates over a range of atmospheric conditions, separate experiments were conducted at low and high relative humidity and using particles mixed with and without secondary organic aerosol. Although particle composition, relative humidity, and secondary organic aerosol all influence the reaction rates,the unsaturated compounds were rapidly oxidized in every experiment. At typical summertime conditions, palmitoleic acid, oleic acid and cholesterol are estimated to have a chemical lifetime of about one day. The experimentally determined reaction rates are used in conjunction with the chemical mass balance model to investigate the effects of aging on source apportionment estimates. The results highlight that assumptions regarding the photochemical stability of molecular markers can lead to substantial biases in predictions of receptor models.