α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NOx environments
N. C. Eddingsaas, C. L. Loza, L. D. Yee, M. Chan, K. A. Schilling, P. S. Chhabra, J. H. Seinfeld, P. O. Wennberg
2012
Atmospheric Chemistry and Physics
<p><strong>Abstract.</strong> The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O<sub>3</sub> in the atmosphere followed by reactions with both HO<sub>2</sub> and NO. Due to the large number of potential reaction
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... ways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low- and high-NO<sub>x</sub> OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O<sub>3</sub> concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO<sub>2</sub>) reacted primarily with either HO<sub>2</sub> under low-NO<sub>x</sub> conditions or NO under high-NO<sub>x</sub> conditions. SOA yield was suppressed under conditions of high-NO<sub>x</sub>. SOA yield under high-NO<sub>x</sub> conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO<sub>x</sub> conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO<sub>x</sub> products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO<sub>x</sub> conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols.</p>
doi:10.5194/acp-12-7413-2012
fatcat:3ehs44d5jbektizc5zef3pshxy