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Environ Sci Technol


Title:Time-Resolved Molecular Characterization of Secondary Organic Aerosol Formed from OH and NO(3) Radical Initiated Oxidation of a Mixture of Aromatic Precursors
Author(s):Kumar V; Slowik JG; Baltensperger U; Prevot ASH; Bell DM;
Address:"Laboratory of Atmospheric Chemistry, Paul Scherrer Institute (PSI), Villigen 5232, Switzerland"
Journal Title:Environ Sci Technol
Year:2023
Volume:20230726
Issue:31
Page Number:11572 - 11582
DOI: 10.1021/acs.est.3c00225
ISSN/ISBN:1520-5851 (Electronic) 0013-936X (Print) 0013-936X (Linking)
Abstract:"Aromatic hydrocarbons (ArHCs) and oxygenated aromatic hydrocarbons (ArHC-OHs) are emitted from a variety of anthropogenic activities and are important precursors of secondary organic aerosol (SOA) in urban areas. Here, we analyzed and compared the composition of SOA formed from the oxidation of a mixture of aromatic VOCs by OH and NO(3) radicals. The VOC mixture was composed of toluene (C(7)H(8)), p-xylene + ethylbenzene (C(8)H(10)), 1,3,5-trimethylbenzene (C(9)H(12)), phenol (C(6)H(6)O), cresol (C(7)H(8)O), 2,6-dimethylphenol (C(8)H(10)O), and 2,4,6-trimethylphenol (C(9)H(12)O) in a proportion where the aromatic VOCs were chosen to approximate day-time traffic-related emissions in Delhi, and the aromatic alcohols make up 20% of the mixture. These VOCs are prominent in other cities as well, including those influenced by biomass combustion. In the NO(3) experiments, large contributions from C(x)H(y)O(z)N dimers (C(15)-C(18)) were observed, corresponding to fast SOA formation within 15-20 min after the start of chemistry. Additionally, the dimers were a mixture of different combinations of the initial VOCs, highlighting the importance of exploring SOAs from mixed VOC systems. In contrast, the experiments with OH radicals yielded gradual SOA mass formation, with C(x)H(y)O(z) monomers (C(6)-C(9)) being the dominant constituents. The evolution of SOA composition with time was tracked and a fast degradation of dimers was observed in the NO(3) experiments, with concurrent formation of monomer species. The rates of dimer decomposition in NO(3) SOA were approximately 2-3 times higher compared to those previously determined for alpha-pinene + O(3) SOA, highlighting the dependence of particle-phase reactions on VOC precursors and oxidants. In contrast, the SOA produced in the OH experiments did not dramatically change over the same time frame. No measurable effects of humidity were observed on the composition and evolution of SOA"
Keywords:"*Air Pollutants/analysis *Volatile Organic Compounds/chemistry Aerosols/analysis *Hydrocarbons, Aromatic Toluene SOA composition aromatic VOCs aromatic oxidation extractive electrospray ionization intra-particle reactions secondary organic aerosol;"
Notes:"MedlineKumar, Varun Slowik, Jay G Baltensperger, Urs Prevot, Andre S H Bell, David M eng Research Support, Non-U.S. Gov't 2023/07/27 Environ Sci Technol. 2023 Aug 8; 57(31):11572-11582. doi: 10.1021/acs.est.3c00225. Epub 2023 Jul 26"

 
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