Journal article

Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: Aircraft vertical profiles in Houston, TX

Brown S, Dubé W, Bahreini R, Middlebrook A, Brock C, Warneke C, De Gouw J, Washenfelder R, Atlas E, Peischl J, Ryerson T, Holloway J, Schwarz J, Spackman R, Trainer M, Parrish D, Fehshenfeld F, Ravishankara A ...see all

Atmospheric Chemistry and Physics, vol. 13, issue 22 (2013) pp. 11317-11337

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Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a poten-tially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime ver-tical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen ox-ides. The latter category serves as a source of the nitrate rad-ical, NO 3 , a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the noctur-nal boundary layer (NBL), which varied in depth from 100– 400 m. Despite concentrated NO x at low altitude, ozone was never titrated to zero, resulting in rapid NO 3 radical pro-duction rates of 0.2–2.7 ppbv h −1 within the NBL. Monoter-penes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1 ppbv h −1), mainly by NO 3 and to a lesser extent O 3 . Concurrent enhancement in organic and nitrate aerosol on several profiles was consis-tent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Some profiles may have been influenced by biomass burning sources as well, making quantitative attribution of organic aerosol sources difficult. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 µg m −3 OA/ppmv CO. A box model simulation in-corporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA pro-duction of 0.5 to 9 µg m −3 .

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