title: Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets.
abstract: 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 (∼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.
authors.affiliation: Department of Atmospheric Sciences, University of Washington, Seattle, WA 98195;
authors.forename: Ben H
authors.identifier: http://orcid.org/0000-0002-5057-2168
authors.initials: BH
authors.lastname: Lee
authors.affiliation: Department of Atmospheric Sciences, University of Washington, Seattle, WA 98195;
authors.forename: Claudia
authors.initials: C
authors.lastname: Mohr
authors.affiliation: Department of Atmospheric Sciences, University of Washington, Seattle, WA 98195;
authors.forename: Felipe D
authors.initials: FD
authors.lastname: Lopez-Hilfiker
authors.affiliation: Department of Chemistry and Molecular Biology, Atmospheric Science, University of Gothenburg, SE-41296 Gothenburg, Sweden;
authors.forename: Anna
authors.initials: A
authors.lastname: Lutz
authors.affiliation: Department of Chemistry and Molecular Biology, Atmospheric Science, University of Gothenburg, SE-41296 Gothenburg, Sweden;
authors.forename: Mattias
authors.initials: M
authors.lastname: Hallquist
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720;
authors.forename: Lance
authors.initials: L
authors.lastname: Lee
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720;
authors.forename: Paul
authors.initials: P
authors.lastname: Romer
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720;
authors.forename: Ronald C
authors.initials: RC
authors.lastname: Cohen
authors.affiliation: Department of Chemistry, Laboratory of Physical Chemistry, University of Helsinki, Helsinki FIN-00014, Finland;
authors.forename: Siddharth
authors.initials: S
authors.lastname: Iyer
authors.affiliation: Department of Chemistry, Laboratory of Physical Chemistry, University of Helsinki, Helsinki FIN-00014, Finland;
authors.forename: Theo
authors.initials: T
authors.lastname: Kurtén
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO 80309; Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80309;
authors.forename: Weiwei
authors.initials: W
authors.lastname: Hu
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO 80309; Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80309;
authors.forename: Douglas A
authors.initials: DA
authors.lastname: Day
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO 80309; Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80309;
authors.forename: Pedro
authors.initials: P
authors.lastname: Campuzano-Jost
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO 80309; Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80309;
authors.forename: Jose L
authors.initials: JL
authors.lastname: Jimenez
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332;
authors.forename: Lu
authors.initials: L
authors.lastname: Xu
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332; School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332;
authors.forename: Nga Lee
authors.initials: NL
authors.lastname: Ng
authors.affiliation: School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332;
authors.forename: Hongyu
authors.initials: H
authors.lastname: Guo
authors.affiliation: School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332;
authors.forename: Rodney J
authors.initials: RJ
authors.lastname: Weber
authors.affiliation: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80309; Chemical Sciences Division, National Oceanic and Atmospheric Administration, Boulder, CO 80305;
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Wild
authors.affiliation: Chemical Sciences Division, National Oceanic and Atmospheric Administration, Boulder, CO 80305;
authors.forename: Steven S
authors.initials: SS
authors.lastname: Brown
authors.affiliation: Chemical Sciences Division, National Oceanic and Atmospheric Administration, Boulder, CO 80305;
authors.forename: Abigail
authors.initials: A
authors.lastname: Koss
authors.affiliation: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80309; Chemical Sciences Division, National Oceanic and Atmospheric Administration, Boulder, CO 80305;
authors.forename: Joost
authors.initials: J
authors.lastname: de Gouw
authors.affiliation: Department of Environmental Science, Policy and Management, University of California, Berkeley, CA 94720;
authors.forename: Kevin
authors.initials: K
authors.lastname: Olson
authors.affiliation: Department of Environmental Science, Policy and Management, University of California, Berkeley, CA 94720;
authors.forename: Allen H
authors.initials: AH
authors.lastname: Goldstein
authors.affiliation: Department of Earth System Science, School of Physical Sciences, University of California, Irvine, CA 92697;
authors.forename: Roger
authors.initials: R
authors.lastname: Seco
authors.affiliation: Department of Earth System Science, School of Physical Sciences, University of California, Irvine, CA 92697;
authors.forename: Saewung
authors.initials: S
authors.lastname: Kim
authors.affiliation: Departments of Chemistry and Earth, Atmospheric and Planetary Sciences and Purdue Climate Change Research Center, Purdue University, West Lafayette, IN 47907;
authors.forename: Kevin
authors.initials: K
authors.lastname: McAvey
authors.affiliation: Departments of Chemistry and Earth, Atmospheric and Planetary Sciences and Purdue Climate Change Research Center, Purdue University, West Lafayette, IN 47907;
authors.forename: Paul B
authors.initials: PB
authors.lastname: Shepson
authors.affiliation: Department of Chemistry, West Chester University, West Chester, PA 19383;
authors.forename: Tim
authors.initials: T
authors.lastname: Starn
authors.affiliation: Atmospheric Research and Analysis, Inc., Cary, NC 27513;
authors.forename: Karsten
authors.initials: K
authors.lastname: Baumann
authors.affiliation: Atmospheric Research and Analysis, Inc., Cary, NC 27513;
authors.forename: Eric S
authors.initials: ES
authors.lastname: Edgerton
authors.affiliation: Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, WA 99352;
authors.forename: Jiumeng
authors.initials: J
authors.lastname: Liu
authors.affiliation: Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, WA 99352;
authors.forename: John E
authors.initials: JE
authors.lastname: Shilling
authors.affiliation: Department of Meteorology, Pennsylvania State University, University Park, PA 16802;
authors.forename: David O
authors.initials: DO
authors.lastname: Miller
authors.affiliation: Department of Meteorology, Pennsylvania State University, University Park, PA 16802;
authors.forename: William
authors.initials: W
authors.lastname: Brune
authors.affiliation: Department of Atmospheric Sciences, University of Washington, Seattle, WA 98195;
authors.forename: Siegfried
authors.initials: S
authors.lastname: Schobesberger
authors.affiliation: Department of Chemistry, University of Washington, Seattle, WA 98195.
authors.forename: Emma L
authors.initials: EL
authors.lastname: D'Ambro
authors.affiliation: Department of Atmospheric Sciences, University of Washington, Seattle, WA 98195; thornton@atmos.washington.edu.
authors.forename: Joel A
authors.initials: JA
authors.lastname: Thornton
keywords: biogenic volatile organic compound oxidation; high-resolution time-of-flight chemical ionization mass spectrometer; lifetime calculation; online measurement; particulate organic nitrates
references.citation: Environ Sci Technol. 2011 Mar 1;45(5):1895-902
references.pmid: 21291229
references.citation: Environ Sci Technol. 2010 Sep 1;44(17):6718-23
references.pmid: 20677734
references.citation: Environ Sci Technol. 2016 Jan 5;50(1):222-31
references.pmid: 26618657
references.citation: Chem Rev. 2013 Aug 14;113(8):5848-70
references.pmid: 23614613
references.citation: Proc Natl Acad Sci U S A. 2015 Jan 6;112(1):37-42
references.pmid: 25535345
references.citation: Nat Chem. 2010 Sep;2(9):713-22
references.pmid: 20729889
references.citation: Environ Sci Technol. 2011 Aug 15;45(16):6908-18
references.pmid: 21732631
references.citation: J Phys Chem A. 2008 Sep 11;112(36):8345-78
references.pmid: 18710205
references.citation: Science. 2012 Sep 7;337(6099):1210-2
references.pmid: 22955831
references.citation: Proc Natl Acad Sci U S A. 2012 Feb 21;109(8):2836-41
references.pmid: 22308444
references.citation: J Phys Chem A. 2014 Mar 6;118(9):1622-37
references.pmid: 24555928
references.citation: Nature. 2014 Feb 27;506(7489):476-9
references.pmid: 24572423
references.citation: Environ Sci Technol. 2014 Oct 7;48(19):11251-8
references.pmid: 25165890
references.citation: Environ Sci Technol. 2010 Jul 15;44(14):5540-5
references.pmid: 20575535
references.citation: Environ Sci Technol. 2014 Oct 21;48(20):11944-53
references.pmid: 25229208
references.citation: Proc Natl Acad Sci U S A. 2010 Apr 13;107(15):6670-5
references.pmid: 20194777
references.citation: Environ Sci Technol. 2014 Jun 3;48(11):6309-17
references.pmid: 24800638