Browsing by Subject "SOA FORMATION"

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  • Kurten, Theo; Moller, Kristian H.; Nguyen, Tran B.; Schwantes, Rebecca H.; Misztal, Pawel K.; Su, Luping; Wennberg, Paul O.; Fry, Juliane L.; Kjaergaard, Henrik G. (2017)
    Oxidation of monoterpenes (C10H16) by nitrate radicals (NO3) constitutes an important source of atmospheric secondary organic aerosol (SOA) and organonitrates. However, knowledge of the mechanisms of their formation is incomplete and differences in yields between similar monoterpenes are poorly understood. In particular, yields of SOA and organonitrates from alpha-pinene + NO3 are low, while those from Delta(3)-carene + NO3 are high. Using computational methods, we suggest that bond scission of the nitrooxy alkoxy radicals from Delta(3)-carene lead to the formation of reactive keto-nitrooxy-alkyl radicals, which retain the nitrooxy moiety and can undergo further reactions to form SOA. By contrast, bond scissions of the nitrooxy alkoxy radicals from alpha-pinene lead almost exclusively to the formation of the relatively unreactive and volatile product pinonaldehyde (C10H16O2), thereby limiting organonitrate and SOA formation. This hypothesis is supported by laboratory experiments that quantify products of the reaction of alpha-pinene + NO3 under atmospherically relevant conditions.
  • Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurten, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A. (2016)
    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 (similar to 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.
  • Ahlberg, Erik; Falk, John; Eriksson, Axel; Holst, Thomas; Brune, William H.; Kristensson, Adam; Roldin, Pontus; Svenningsson, Birgitta (2017)
    The atmospheric organic aerosol is a tremendously complex system in terms of chemical content. Models generally treat the mixtures as ideal, something which has been questioned owing to model-measurement discrepancies. We used an oxidation flow reactor to produce secondary organic aerosol (SOA) mixtures containing oxidation products of biogenic (alpha-pinene, myrcene and isoprene) and anthropogenic (m-xylene) volatile organic compounds (VOCs). The resulting volume concentration and chemical composition was measured using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. The SOA mass yield of the mixtures was compared to a partitioning model constructed from single VOC experiments. The single VOC SOA mass yields with no wall-loss correction applied are comparable to previous experiments. In the mixtures containing myrcene a higher yield than expected was produced. We attribute this to an increased condensation sink, arising from myrcene producing a significantly higher number of nucleation particles compared to the other precursors. Isoprene did not produce much mass in single VOC experiments but contributed to the mass of the mixtures. The effect of high concentrations of isoprene on the OH exposure was found to be small, even at OH reactivities that previously have been reported to significantly suppress OH exposures in oxidation flow reactors. Furthermore, isoprene shifted the particle size distribution of mixtures towards larger sizes, which could be due to a change in oxidant dynamics inside the reactor. (C) 2017 The Authors. Published by Elsevier Ltd.
  • McFiggans, Gordon; Mentel, Thomas F.; Wildt, Juergen; Pullinen, Iida; Kang, Sungah; Kleist, Einhard; Schmitt, Sebastian; Springer, Monika; Tillmann, Ralf; Wu, Cheng; Zhao, Defeng; Hallquist, Mattias; Faxon, Cameron; Le Breton, Michael; Hallquist, Asa M.; Simpson, David; Bergstroem, Robert; Jenkin, Michael E.; Ehn, Mikael; Thornton, Joel A.; Alfarra, M. Rami; Bannan, Thomas J.; Percival, Carl J.; Priestley, Michael; Topping, David; Kiendler-Scharr, Astrid (2019)
    Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene 'scavenges' hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).
  • Yang, Yuan; Wang, Yonghong; Yao, Dan; Zhao, Shuman; Yang, Shuanghong; Ji, Dongsheng; Sun, Jie; Wang, Yinghong; Liu, Zirui; Hu, Bo; Zhang, Renjian; Wang, Yuesi (2020)
    To what extent anthropogenic emissions could influence volatile organic compound (VOCs) concentrations and related atmospheric reactivity is still poorly understood. China's 70th National Day holidays, during which anthropogenic emissions were significantly reduced to ensure good air quality on Anniversary Day, provides a unique opportunity to investigate these processes. Atmospheric oxidation capacity (AOC), OH reactivity, secondary transformation, O-3 formation and VOCs-PM2.5 sensitivity are evaluated based on parameterization methods and simultaneous measurements of VOCs, O-3, NOx, CO, SO2, PM2.5, JO(1)D, JNO(2), JNO(3) carried out at a suburban site between Beijing and Tianjin before, during, and after the National Day holiday 2019. During the National Day holidays, the AOC, OH reactivity, O-3 formation potential (OFP) and secondary organic aerosol formation potential (SOAP) were 1.6 x 10(7) molecules cm(-3) s(-1), 41.8 s(-1), 299.2 mg cm(-3) and 1471.8 mg cm(-3), respectively, which were 42%, 29%, 47% and 42% lower than pre-National Day values and -12%, 42%, 36% and 42% lower than post-National Day values, respectively. Reactions involving OH radicals dominated the AOC during the day, but OH radicals and O-3 reactions at night. Alkanes (the degree of unsaturation = 0, (D, Equation (1)) accounted for the largest contributions to the total VOCs concentration, oxygenated VOCs (OVOCs; D