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Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

Journal article
Authors Cameron Faxon
Julia Hammes
Michael Le Breton
Ravi K. Pathak
Mattias Hallquist
Published in Atmospheric Chemistry And Physics
Volume 18
Pages 5467-5481
ISSN 1680-7316
Publication year 2018
Published at Department of Chemistry and Molecular Biology
Pages 5467-5481
Language en
Subject categories Meteorology and Atmospheric Sciences, Climate Research, Environmental chemistry, Environmental Sciences, Organic Chemistry, Physical Chemistry, Analytical Chemistry, Chemical Sciences


The gas-phase nitrate radical (NO 3 • ) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NO x reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO 3 • with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C 10 H 15 NO 6 , C 10 H 17 NO 6 , C 8 H 11 NO 6 , C 10 H 17 NO 7 , and C 9 H 13 NO 7 ) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO 3 • produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

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