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American Chemical Society, The Journal of Physical Chemistry A, 47(117), p. 12468-12483, 2013

DOI: 10.1021/jp408745h

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Radical Product Yields from the Ozonolysis of Short Chain Alkenes under Atmospheric Boundary Layer Conditions

This paper is available in a repository.
This paper is available in a repository.

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Abstract

The gas-phase reaction of ozone with unsaturated VOCs, alkenes, is an important source of the critical atmospheric oxidant OH, especially at night when other photolytic radical initiation routes cannot occur. Alkene ozonolysis is also known to directly form HO2 radicals, which may be readily converted to OH through reaction with NO, but whose formation is poorly understood. We report a study of the radical (OH, HO2 and RO2) production from a series of small alkenes (propene, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, 2,3-dimethyl-2-butene (tetramethyl ethene, TME) and isoprene). Experiments were performed in the European Photoreactor (EUPHORE) atmospheric simulation chamber, with OH and HO2 levels directly measured by laser-induced fluorescence (LIF), and HO2 +  RO2 levels measured by peroxy-radical chemical amplification (PERCA). OH yields were found to be in good agreement with the majority of previous studies performed under comparable conditions (atmospheric pressure, long timescales) using tracer and scavenger approaches. HO2 yields ranged from 4 % (trans-2-butene) to 34 % (2-methylpropene), lower than previous experimental determinations. Increasing humidity further reduced the HO2 yields obtained, by typically 50 % for an RH increase from 0.5 to 30 %, suggesting that HOx production from alkene ozonolysis may be lower than current models suggest under (humid) ambient atmospheric boundary layer conditions. The mechanistic origin of the OH and HO2 production observed is discussed in the context of previous experimental and theoretical studies.