VOC Composition of Air Masses Transported from Asia to the U.S. West Coast

Airborne measurements of volatile organic compounds (VOCs) were performed using a proton-transfer-reaction mass spectrometer (PTR-MS) operated onboard a NOAA WP-3 aircraft during the Intercontinental Transport and Chemical Transformation (ITCT) experiment in 2002. Enhancements of acetone (CH₃COCH₃), methanol (CH₃OH), acetonitrile (CH₃CN) and in some cases benzene were observed in air masses that were impacted by outflow from Asia. The enhancement ratios with respect to carbon monoxide are compared to emission factors for fossil fuel combustion and biomass burning, which gives some insight into the sources responsible for the pollution. The observed mixing ratios for acetone, methanol and in particular acetonitrile were generally reduced in the marine boundary layer, suggesting the presence of an ocean uptake sink. The ocean uptake of acetonitrile was found to be particularly efficient in a zone with upwelling water off of the U.S. west coast. Reduced mixing ratios of acetone and methanol were observed in a stratospheric intrusion. This observation gives some information about the lifetime of these VOCs in the stratosphere. Enhanced concentrations of aromatic hydrocarbons were observed in air masses that were impacted by urban sources in California. The ratio between the concentrations of benzene, toluene and higher aromatics indicated the degree of photochemical oxidation. PTR-MS only gives information about the mass of the ions produced by proton-transfer reactions between H₃O⁺ and VOCs in the instrument. The identification of VOCs was confirmed by coupling a gas-chromatographic (GC) column to the instrument and post-flight GC-PTR-MS analyses of canister samples collected during the flights.