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Title: Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

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 also estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. In 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.
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  1. Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences
  2. Univ. of Gothenburg (Sweden)
  3. Univ. of California, Berkeley, CA (United States)
  4. Univ. of Helsinki (Finland)
  5. Univ. of Colorado, Boulder, CO (United States)
  6. Georgia Inst. of Technology, Atlanta, GA (United States)
  7. Univ. of Colorado, Boulder, CO (United States); National Oceanic and Atmospheric Administration, Boulder, CO (United States)
  8. National Oceanic and Atmospheric Administration, Boulder, CO (United States)
  9. Univ. of California, Irvine, CA (United States)
  10. Purdue Univ., West Lafayette, IN (United States)
  11. West Chester Univ., PA (United States)
  12. Atmospheric Research and Analysis, Inc., Cary, NC (United States)
  13. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  14. Pennsylvania State Univ., University Park, PA (United States)
  15. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Grant/Contract Number:
SC0011791; SC0004577; SC0006867
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 6; Journal ID: ISSN 0027-8424
National Academy of Sciences, Washington, DC (United States)
Research Org:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org:
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; particulate organic nitrates; online measurement; lifetime calculation; high-resolution time-of-flight chemical ionization mass spectrometer; biogenic volatile organic compound oxidation
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1390589