Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-7-14603-2007
http://www.atmos-chem-phys-discuss.net/7/14603/2007/
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http://www.atmos-chem-phys-discuss.net/7/14603/2007/acpd-7-14603-2007.pdf
14603
14638
2007-10-15
The ozonolysis of primary aliphatic amines in single and multicomponent fine particles
J. Zahardis
S. Geddes
G. A. Petrucci
giuseppe.petrucci@uvm.edu
Department of Chemistry, University of Vermont, Burlington, VT 05405, USA
The oxidative processing by ozone of the particulate amines octadecylamine
(ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines
resulted in strong NO<sub>2</sub><sup>−</sup> and NO<sub>3</sub><sup>−</sup> ion signals that
increased with ozone exposure as monitored by photoelectron resonance
capture ionization aerosol mass spectrometry. These products suggest a
mechanism of progressive oxidation of the particulate amines to nitro
alkanes. Additionally, a strong ion signal at 125 <i>m/z</i> is assigned to the ion
NO<sub>3</sub><sup>−</sup>(HNO<sub>3</sub>). For ozonized mixed particles containing ODA or
HDA + oleic acid (OL), with p<sub>O3</sub>≥3×10<sup/>−7</sup> atm, imine,
secondary amide, and tertiary amide products were measured. These products
most likely arise from reactions of amines with aldehydes (for imines) and
stabilized Criegee intermediates (SCI) or secondary ozonides (for amides)
from the fatty acid. The routes to amides via SCI and/or secondary ozonides
was shown to be more important than comparable amide forming reactions
between amines and organic acids, using azelaic acid as a test compound.
Finally, direct evidence is provided for the formation of a surface barrier
in the ODA + OL reaction system that resulted in the retention of OL at high
ozone exposures (up to 10<sup>−3</sup> atm for 17 s). This effect was not observed
in HDA + OL or single component OL particles, suggesting that it may be a
species-specific surfactant effect from an in situ generated amide or imine.
Implications to tropospheric chemistry, including particle bound amines as
sources of oxidized gas phase nitrogen species (e.g. NO<sub>2</sub>, NO<sub>3</sub>),
formation of nitrogen enriched HULIS via ozonolysis of amines and source
apportionment are discussed.
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