TY - JOUR

T1 - Highly functionalized organic nitrates in the southeast United States

T2 - contribution to secondary organic aerosol and reactive nitrogen budgets

AU - Lee, Ben H.

AU - Mohr, Claudia

AU - Lopez-Hilfiker, Felipe D.

AU - Lutz, Anna

AU - Hallquist, Mattias

AU - Lee, Lance

AU - Romer, Paul

AU - Cohen, Ronald C.

AU - Iyer, Siddharth

AU - Kurtén, Theo

AU - Hu, Weiwei

AU - Day, Douglas A.

AU - Campuzano-Jost, Pedro

AU - Jimenez, Jose L.

AU - Xu, Lu

AU - Ng, Nga Lee

AU - Guo, Hongyu

AU - Weber, Rodney J.

AU - Wild, Robert J.

AU - Brown, Steven S.

AU - Koss, Abigail

AU - de Gouw, Joost

AU - Olson, Kevin

AU - Goldstein, Allen H.

AU - Seco, Roger

AU - Kim, Saewung

AU - McAvey, Kevin

AU - Shepson, Paul B.

AU - Starn, Tim

AU - Baumann, Karsten

AU - Edgerton, Eric S.

AU - Liu, Jiumeng

AU - Shilling, John E.

AU - Miller, David O.

AU - Brune, William

AU - Schobesberger, Siegfried

AU - D'Ambro, Emma L.

AU - Thornton, Joel A.

PY - 2016

Y1 - 2016

N2 - Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas- particle equilibrium and (ii) have a short particle-phase lifetime (2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

AB - Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas- particle equilibrium and (ii) have a short particle-phase lifetime (2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

KW - Biogenic volatile organic compound oxidation

KW - High-resolution time-of-flight chemical ionization mass spectrometer

KW - Lifetime calculation

KW - Online measurement

KW - Particulate organic nitrates

U2 - 10.1073/pnas.1508108113

DO - 10.1073/pnas.1508108113

M3 - Journal article

AN - SCOPUS:84957824514

VL - 113

SP - 1516

EP - 1521

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

SN - 0027-8424

IS - 6

ER -