Photochemical aging of atmospherically reactive organic compounds involving brown carbon at the air-aqueous interface

Water-soluble brown carbon in the aqueous core of aerosol may play a role in the photochemical aging of organic film on the aerosol surface. To better understand the reactivity and photochemical aging processes of organic coating on the aqueous aerosol surface, we have simulated the photosensitized reaction of organic films made of several long-chain fatty acids in a Langmuir trough in the presence or absence of irradiation. Several chemicals (imidazole-2-carboxaldehyde and humic acid), PM2:5 samples collected from the field, and secondary organic aerosol samples generated from a simulation chamber were used as photosensitizers to be involved in the photochemistry of the organic films. Stearic acid, elaidic acid, oleic acid, and two different phospholipids with the same carbon chain length and different degrees of saturation, i.e. 1,2-distearoylsn-glycero-3-phosphocholine (DSPC) and 1,2-dioleoylsnglycero-3-phosphocholine (DOPC), were chosen as the common organic film-forming species in this analysis. The double bond (trans and cis) in unsaturated organic compounds has an effect on the surface area of the organic monolayer. The oleic acid (OA) monolayer possessing a cis double bond in an alkyl chain is more expanded than elaidic acid (EA) monolayers on artificial seawater that contain a photosensitizer. Monitoring the change in the relative area of DOPC monolayers has shown that DOPC does not react with photosensitizers under dark conditions. Instead, the photochemical reaction initiated by the excited photosensitizer and molecular oxygen can generate new unsaturated products in the DOPC monolayers, accompanied by an increase in the molecular area. The DSPC monolayers did not yield any photochemical oxidized products under the same conditions. The spectra measured with polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) were also consistent with the results of a surface pressure-area isotherm. Here, a reaction mechanism explaining these observations is presented and discussed. The results of PM_2:5 and SOA samples will contribute to our understanding of the processing of organic aerosol aging that alters the aerosol composition.