Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.
SignificanceAerosol particles can form and grow by gas-to-particle conversion and eventually act as seeds for cloud droplets, influencing global climate. Volatile organic compounds emitted from plants are oxidized in the atmosphere, and the resulting products drive particle growth. We measure particle growth by oxidized biogenic vapors with a well-controlled laboratory setup over a wide range of tropospheric temperatures. While higher temperatures lead to increased reaction rates and concentrations of highly oxidized molecules, lower temperatures allow additional, but less oxidized, species to condense. We measure rapid growth over the full temperature range of our study, indicating that organics play an important role in aerosol growth throughout the troposphere. Our finding will help to sharpen the predictions of global aerosol models.
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