Journal ArticleDOI
Time-resolved molecular characterization of limonene/ozone aerosol using high-resolution electrospray ionization mass spectrometry
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The data are consistent with fast production of the first-generation SOA constituents, including oligomers, followed by very slow aging processes that have a relatively small effect on the average molecular composition on the timescale of the authors' experiments.Abstract:
Molecular composition of limonene/O3 secondary organic aerosol (SOA) was investigated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) as a function of reaction time. SOA was generated by ozonation of D-limonene in a reaction chamber and sampled at different time intervals using a cascade impactor. The SOA samples were extracted into acetonitrile and analyzed using a HR-ESI-MS instrument with a resolving power of 100 000 (m/Δm). The resulting mass spectra provided detailed information about the extent of oxidation inferred from the O : C ratios, double bond equivalency (DBE) factors, and aromaticity index (AI) values in hundreds of identified individual SOA species. The chemical composition of SOA was approximately the same for all size-fractionated samples studied in this experiment (0.05 to 0.5 μm range). The SOA constituents quickly reached an average O : C ratio of 0.43, which grew to 0.46 after one hour of additional oxidation of particles by the excess ozone. The dominant mechanism of oligomerization, inferred from high resolution ESI-MS data, was reaction between Criegee intermediates and stable first-generation products of limonene ozonolysis. Although the SOA composition was dominated by various oxidized aliphatic compounds, a small fraction of products appeared to contain aromatic rings. SOA generation was also studied in the presence of UV radiation and at elevated relative humidity (RH). The presence of UV radiation had a negligible effect on the SOA composition. The presence of water vapor resulted in a slight redistribution of peak intensities in the mass spectrum likely arising from hydration of certain SOA constituents. The data are consistent with fast production of the first-generation SOA constituents, including oligomers, followed by very slow aging processes that have a relatively small effect on the average molecular composition on the timescale of our experiments.read more
Citations
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Journal ArticleDOI
Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol
Jesse H. Kroll,Neil M. Donahue,Jose L. Jimenez,Sean H. Kessler,Manjula R. Canagaratna,Kevin R. Wilson,Katye E. Altieri,Lynn Mazzoleni,Andrew S. Wozniak,Hendrik Bluhm,Erin R. Mysak,Erin R. Mysak,Jared D. Smith,Jared D. Smith,Charles E. Kolb,Douglas R. Worsnop +15 more
TL;DR: The utility of describing organic aerosol in terms of average carbon oxidation state, a quantity that always increases with oxidation, is demonstrated and is readily measured using state-of-the-art analytical techniques.
Journal ArticleDOI
Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications
Manjula R. Canagaratna,Jose L. Jimenez,Jesse H. Kroll,Qi Chen,Sean H. Kessler,Paola Massoli,L. Hildebrandt Ruiz,Edward C. Fortner,Leah R. Williams,Kevin R. Wilson,Jason D. Surratt,Neil M. Donahue,J. T. Jayne,D. R. Worsnop +13 more
TL;DR: Aiken et al. as mentioned in this paper used the Aerodyne high-resolution time-of-flight mass spectrometer (HR-ToF-AMS) to measure OA elemental composition.
Journal Article
Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol
TL;DR: In this article, the authors demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques.
Journal ArticleDOI
Tropospheric aqueous-phase chemistry: kinetics, mechanisms, and its coupling to a changing gas phase.
Hartmut Herrmann,Thomas Schaefer,Andreas Tilgner,Sarah A. Styler,Christian E. Weller,Monique Teich,Tobias Otto +6 more
Journal ArticleDOI
A simplified description of the evolution of organic aerosol composition in the atmosphere
Colette L. Heald,Jesse H. Kroll,Jose L. Jimenez,Kenneth S. Docherty,Peter F. DeCarlo,Peter F. DeCarlo,Allison C. Aiken,Allison C. Aiken,Qi Chen,Scot T. Martin,Delphine K. Farmer,Paulo Artaxo +11 more
TL;DR: In this paper, the bulk composition of organic aerosol from a variety of environments (laboratory and field) occupies a narrow range in the space of a Van Krevelen diagram (H:C versus O:C), characterized by a slope of ∼−1.
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