Competition between atmospherically relevant fatty acid monolayers at the air/water interface.

Competition and oxidation of fatty acids spread at the air/water interface were investigated using surface-specific, broad-bandwidth, sum frequency generation spectroscopy. At the air/water interface, a monolayer of oleic acid replaced a monolayer of deuterated palmitic acid at equilibrium spreading pressure. Subsequent oxidation of the oleic acid monolayer with ozone resulted in products more water soluble than the palmitic acid; therefore, the palmitic acid monolayer reformed at the surface. Results indicate that the surfactants on the surface of fat-coated tropospheric aerosols will only possess oxidized acyl chains after all less soluble species in the aqueous subphase have been removed through the processes of replacement at the surface and atmospheric oxidation.