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Effect of NOx on 1,3,5-trimethylbenzene (TMB) oxidation product distribution and particle formation

Journal article
Authors Epameinondas Tsiligiannis
Julia Hammes
Christian Mark Salvador
Thomas Mentel
Mattias Hallquist
Published in Atmospheric Chemistry And Physics
Volume 19
Issue 23
Pages 15073–15086
ISSN 1680-7316
Publication year 2019
Published at Department of Chemistry and Molecular Biology
Pages 15073–15086
Language en
Links https://doi.org/10.5194/acp-19-1507...
Keywords 1,3,5-trimethylbenzene, TMB, new particle formation, NPF, highly oxygenated organic molecules, HOM, organonitrates, OH oxidation, NOx, anthropogenic volatile organic compounds, chemical ionization mass spectrometry, CIMS, Go:PAM, Gothenburg potential aerosol mass, flow reactor.
Subject categories Chemical Sciences, Analytical Chemistry, Organic Chemistry, Other Chemistry Topics, Earth and Related Environmental Sciences, Climate Research, Environmental Sciences, Environmental chemistry, Meteorology and Atmospheric Sciences

Abstract

Secondary organic aerosol (SOA) represents a significant fraction of the tropospheric aerosol and its precursors are volatile organic compounds (VOCs). Anthropogenic VOCs (AVOC) dominate the VOC budget in many urban areas with 1,3,5-trimethylbenzene (TMB) being among the most reactive aromatic AVOCs. TMB formed highly oxygenated organic molecules (HOMs) in an NOx-free environment, which could contribute to new particle formation (NPF) depending on oxidation conditions where elevated OH oxidation enhanced particle formation. The experiments were performed in an oxidation flow reactor, the Go:PAM unit, under controlled OH oxidation conditions. By addition of NOx to the system we investigated the effect of NOx on particle formation and on the product distribution. We show that the formation of HOMs, and especially HOM accretion products, strongly varies with NOx conditions. We observe a suppression of HOM and particle formation with increasing NOx/ΔTMB ratio and an increase in the formation of organonitrates (ONs) mostly at the expense of HOM accretion products. We propose reaction mechanisms and pathways that explain the formation and observed product distributions with respect to oxidation conditions. We hypothesise that, based on our findings from TMB oxidation studies, aromatic AVOCs may not contribute significantly to NPF under typical NOx/AVOC conditions found in urban atmospheres.

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