Journal cover Journal topic
Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
Atmos. Chem. Phys., 15, 12867-12877, 2015
http://www.atmos-chem-phys.net/15/12867/2015/
doi:10.5194/acp-15-12867-2015
© Author(s) 2015. This work is distributed
under the Creative Commons Attribution 3.0 License.
Research article
19 Nov 2015
Laboratory evidence of organic peroxide and peroxyhemiacetal formation in the aqueous phase and implications for aqueous OH
Y. B. Lim1,a and B. J. Turpin2 1Department of Environmental Sciences, Rutgers University, New Brunswick, NJ, USA
2Department of Environmental Science and Engineering, University of North Carolina, Chapel Hill, NC 27599, USA
anow at: Center for Environmental, Health and Welfare Research, Korea Institute of Science and Technology, Seoul, Republic of Korea
Abstract. Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is considered a potentially important atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2–C3) are precursors for SOAaq; products include organic acids, organic sulfates, and high-molecular-weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior.

This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra-high-resolution Fourier transform ion cyclotron resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals and epoxides (i.e., IEPOX), and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.


Citation: Lim, Y. B. and Turpin, B. J.: Laboratory evidence of organic peroxide and peroxyhemiacetal formation in the aqueous phase and implications for aqueous OH, Atmos. Chem. Phys., 15, 12867-12877, doi:10.5194/acp-15-12867-2015, 2015.
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This paper demonstrates organic peroxide and peroxyhemiacetal formation during aqueous photooxidation of methylglyoxal using ultra-high-resolution Fourier transform ion cyclotron resonance electrospray ionization mass spectrometry (FTICR-MS). Then, we provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous secondary organic aerosol (SOA).
This paper demonstrates organic peroxide and peroxyhemiacetal formation during aqueous...
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