Emissions and photochemistry of oxygenated VOCs in urban plumes in the Northeastern United States

Abstract

Abstract. Photochemical processes inside urban plumes in the Northeast of the United States have been studied using a highly detailed chemical model, based upon the Master Chemical Mechanism (MCM). The model results have been compared to measurements of oxygenated VOCs (acetone, methyl ethyl ketone, acetaldehyde, acetic acid and methanol) obtained during several flights of the NOAA WP-3D aircraft, which sampled plumes from the New York City area during the ICARTT campaign in 2004. The agreement between the model and the measurements was within 40–60% for all species, except acetic acid. The model results have been used to study the formation and photochemical evolution of acetone, methyl ethyl ketone and acetaldehyde. Under the conditions encountered during the ICARTT campaign, acetone is produced from the oxidation of propane (24–28%) and i-propanol (<15%) and from a number of products of i-pentane oxidation. Methyl ethyl ketone (MEK) is mostly produced from the oxidation of n-butane (20–30%) and 3-methylpentane (<40%). Acetaldehyde is formed from several precursors, mostly small alkenes, >C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 6–23% and 5–25% of acetaldehyde photochemical formation. The results highlight the importance of long-chain alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.