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Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases

Qiu, Junting and Liang, Zhancong and Tonokura, Kenichi and Colussi, Agustín J. and Enami, Shinichi (2020) Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases. Environmental Science and Technology, 54 (7). pp. 3890-3899. ISSN 0013-936X. https://resolver.caltech.edu/CaltechAUTHORS:20200306-081509744

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Abstract

The α-hydroxyalkyl-hydroperoxides [R–(H)C(−OH)(−OOH), α-HH] produced in the ozonolysis of unsaturated organic compounds may contribute to secondary organic aerosol (SOA) aging. α-HHs’ inherent instability, however, hampers their detection and a positive assessment of their actual role. Here we report, for the first time, the rates and products of the decomposition of the α-HHs generated in the ozonolysis of atmospherically important monoterpenes α-pinene (α-P), d-limonene (d-L), γ-terpinene (γ-Tn), and α-terpineol (α-Tp) in water/acetonitrile (W/AN) mixtures. We detect α-HHs and multifunctional decomposition products as chloride adducts by online electrospray ionization mass spectrometry. Experiments involving D₂O and H₂¹⁸O, instead of H₂¹⁶O, and an OH-radical scavenger show that α-HHs decompose into gem-diols + H₂O₂ rather than free radicals. α-HHs decay mono- or biexponentially depending on molecular structure and solvent composition. e-Fold times, τ_(1/e), in water-rich solvent mixtures range from τ_(1/e) = 15–45 min for monoterpene-derived α-HHs to τ_(1/e) > 10³ min for the α-Tp-derived α-HH. All τ_(1/e)’s dramatically increase in <20% (v/v) water. Decay rates of the α-Tp-derived α-HH in pure water increase at lower pH (2.3 ≤ pH ≤ 3.3). The hydroperoxides detected in day-old SOA samples may reflect their increased stability in water-poor media and/or the slow decomposition of α-HHs from functionalized terpenes.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.est.9b07497DOIArticle
ORCID:
AuthorORCID
Tonokura, Kenichi0000-0003-1910-8508
Colussi, Agustín J.0000-0002-3400-4101
Enami, Shinichi0000-0002-2790-7361
Additional Information:© 2020 American Chemical Society. Received: December 9, 2019; Revised: February 28, 2020; Accepted: March 4, 2020; Published: March 4, 2020. S.E. is grateful to the JSPS KAKENHI Grant No. 19H01154. A.J.C. acknowledges support from the National Science Foundation U.S.A., Grant AGS-1744353. Author Contributions: S.E. designed research, J.Q., Z.L., and S.E. performed experiments, and S.E. contributed new reagents/analytical tools. All authors analyzed data and wrote the paper. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)19H01154
NSFAGS-1744353
Issue or Number:7
Record Number:CaltechAUTHORS:20200306-081509744
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200306-081509744
Official Citation:Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases. Junting Qiu, Zhancong Liang, Kenichi Tonokura, Agustín J. Colussi, and Shinichi Enami. Environmental Science & Technology 2020 54 (7), 3890-3899; DOI: 10.1021/acs.est.9b07497
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:101733
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Mar 2020 17:13
Last Modified:08 Apr 2020 17:15

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