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

by R. Sommariva, J. A. De Gouw, M. Trainer, E. Atlas, P. D. Goldan, W. C. Kuster, C. Warneke, F. C. Fehsenfeld
Atmospheric Chemistry and Physics ()
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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 4060 % 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 (2428 and i-propanol (C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 623 % and 525 % of acetaldehyde photochemical formation. The results highlight the importance of alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.

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