Secondary Organic Aerosol Formation from High-NOx Photo-Oxidation of Low Volatility Precursors: n-Alkanes

Presto, Albert A.; Miracolo, Marissa A.; Donahue, Neil M.; Robinson, Allen L.

doi:10.1021/es903712r

Cited by 202 publications

(307 citation statements)

References 41 publications

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“…Similar products have been identified in the laboratory under high NO x conditions (Lim and Ziemann, 2005;Presto et al, 2010), and also in polluted urban conditions. Russell et al (2011) observed negligible organonitrates in a wide range of aerosol samples including from Mexico City, and attributed their absence to inaerosol hydrolysis in humid conditions.…”

Section: Specific Chemical Identity Of Aerosol Constituentssupporting

confidence: 70%

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

et al. 2011

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Abstract. The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 µg m −3 , and SOA peaking at 10-15 µg m −3 during mid-day. The majority (≥75 %) of the model SOA stems from reaction products of the large n-alkanes, used here as surrogates for all emitted hydrocarbons of similar volatility, with the remaining SOA originating mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by δ-hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA Correspondence to: J. Lee-Taylor (julial@ucar.edu) mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

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Section: Specific Chemical Identity Of Aerosol Constituentssupporting

confidence: 70%

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

et al. 2011

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“…For the oxidation products of C 15 H 32 , SOA mass yields were taken from Presto et al (2010): 0.044, 0.071, 0.41, and 0.30 for the 0.1, 1, 10, and 100 µg m −3 bins, respectively (Presto et al, 2010, did not report a yield for the 1000 µg m −3 bin). These yields are reported for SOA with unit density (1 g cm −3 ).…”

Section: Additional Ivocs From Dieselmentioning

confidence: 99%

Simulating secondary organic aerosol from missing diesel-related intermediate-volatility organic compound emissions during the Clean Air for London (ClearfLo) campaign

et al. 2016

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Abstract. We present high-resolution (5 km × 5 km) atmospheric chemical transport model (ACTM) simulations of the impact of newly estimated traffic-related emissions on secondary organic aerosol (SOA) formation over the UK for 2012. Our simulations include additional diesel-related intermediate-volatility organic compound (IVOC) emissions derived directly from comprehensive field measurements at an urban background site in London during the 2012 Clean Air for London (ClearfLo) campaign. Our IVOC emissions are added proportionally to VOC emissions, as opposed to proportionally to primary organic aerosol (POA) as has been done by previous ACTM studies seeking to simulate the effects of these missing emissions. Modelled concentrations are evaluated against hourly and daily measurements of organic aerosol (OA) components derived from aerosol mass spectrometer (AMS) measurements also made during the ClearfLo campaign at three sites in the London area. According to the model simulations, diesel-related IVOCs can explain on average ∼ 30 % of the annual SOA in and around London. Furthermore, the 90th percentile of modelled daily SOA concentrations for the whole year is 3.8 µg m −3 , constituting a notable addition to total particulate matter. More measurements of these precursors (currently not included in official emissions inventories) is recommended. During the period of concurrent measurements, SOA concentrations at the Detling rural background location east of London were greater than at the central London location. The model shows that this was caused by an intense pollution plume with aPublished by Copernicus Publications on behalf of the European Geosciences Union. 6454 R. Ots et al.: Simulating SOA from missing diesel-related IVOC emissions in London strong gradient of imported SOA passing over the rural location. This demonstrates the value of modelling for supporting the interpretation of measurements taken at different sites or for short durations.

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“…The carbon number and structure of an alkane influences its SOA mass yield; for the same structure the SOA potential increases with carbon number (Lim and Ziemann, 2009;Presto et al, 2010), while for the same carbon number cyclic alkanes form the most SOA followed by linear and then branched alkanes (Lim and Ziemann, 2009;Tkacik et al, 2012). However, in 3-D models that employ SAPRC-11, a single model VOC species, ALK5, is used to describe the SOA formation from alkanes roughly larger than a carbon number of 6.…”

Section: Emissionsmentioning

confidence: 99%

Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

et al. 2015

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Abstract. Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multigenerational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT (University of California, Davis/California Institute of Technology) air quality model. In the SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory smog chamber data for each precursor/compound class. SOM was installed in the UCD/CIT model, which simulated air quality over 2-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-tocarbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of organic aerosol.

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Secondary Organic Aerosol Formation from High-NO_x Photo-Oxidation of Low Volatility Precursors: n-Alkanes

Cited by 202 publications

References 41 publications

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

Simulating secondary organic aerosol from missing diesel-related intermediate-volatility organic compound emissions during the Clean Air for London (ClearfLo) campaign

Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

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