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Molecular characterization of S‐ and N‐containing organic constituents in ambient aerosols by negative ion mode high‐resolution Nanospray Desorption Electrospray Ionization Mass Spectrometry: CalNex 2010 field study
Author(s) -
O'Brien Rachel E.,
Laskin Alexander,
Laskin Julia,
Rubitschun Caitlin L.,
Surratt Jason D.,
Goldstein Allen H.
Publication year - 2014
Publication title -
journal of geophysical research: atmospheres
Language(s) - English
Resource type - Journals
eISSN - 2169-8996
pISSN - 2169-897X
DOI - 10.1002/2014jd021955
Subject(s) - chemistry , mass spectrometry , analytical chemistry (journal) , electrospray ionization , mass spectrum , chemical ionization , nitrogen , environmental chemistry , ion , ionization , chromatography , organic chemistry
Samples of ambient aerosols from the 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field study were analyzed using negative ion mode Nanospray Desorption Electrospray Ionization High‐Resolution Mass Spectrometry (nano‐DESI/MS). Four samples per day (6 h each) were collected in Bakersfield, CA on 20–24 June. Four characteristic groups were identified: molecules composed of carbon, hydrogen, and oxygen only (CHO), sulfur‐ (CHOS), nitrogen‐ (CHON), and both nitrogen‐ and sulfur‐containing organics (CHONS). The chemical formula and elemental ratios were consistent with the presence of organonitrates, organosulfate, and nitroxy organosulfates in the negative ion mode mass spectra. The number of observed CHO compounds increased in the afternoon samples, suggesting photochemical processing as a source. The average number of CHOS compounds had the smallest changes during the day, consistent with a more broadly distributed source. Both of the nitrogen‐containing groups (CHONS and CHON) had greater numbers of compounds in the early morning (midnight to 6 A.M.) and night (6 P.M. to midnight) samples, respectively, consistent with nitrate radical chemistry as a likely source for those compounds. Most of the compounds were found in submicron particles. The size distribution of the number of CHON compounds was bimodal, potentially indicating two types of sources. We conclude that the majority of the compounds observed were secondary in nature with both biogenic and anthropogenic sources. These data are complementary to previous results from positive ion mode nano‐DESI/MS analysis of a subset of the same samples providing a more complete view of aerosol chemical composition at Bakersfield.