Fates of Organic Hydroperoxides in Atmospheric Condensed Phases

Enami, Shinichi

doi:10.1021/acs.jpca.1c01513

Cited by 29 publications

(67 citation statements)

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“…Importantly, H 2 O 2 is produced not only by H + -catalyzed decomposition of α-HHs but also by decomposition of α-acyloxyalkyl-hydroperoxides, 38 α-alkoxyalkyl-hydroperoxides, 11 and likely highly oxygenated organic molecules (HOMs) in aqueous media. 1,38 Recent field measurements revealed that the decomposition of organic peroxides is the dominant source of aerosol-phase H 2 O 2 . 39,40 Thus, our results shed new light on the mechanism of formation of radicals in particulate matter-dissolved water reported in the literature.…”

Section: Atmospheric Implicationsmentioning

confidence: 99%

“…Atmospheric oxidation of volatile organic compounds by both hydroxyl (OH) radicals and ozone produces organic hydroperoxides (ROOHs), which are taken up into atmospheric condensed phases such as aqueous aerosols, secondary organic aerosols (SOAs), and cloud/fog droplets. 1 Because ROOHs are highly reactive, they are expected to contribute to changes in the oxidative and toxicological potentials of atmospheric particulate matter. Atmospheric model simulations have predicted that ROOHs account for up to 60% of global SOAs.…”

Section: Introductionmentioning

confidence: 99%

“…Recent studies revealed that liquid-phase α-HHs decompose to the corresponding aldehydes and H 2 O 2 at a rate that depends sensitively on the water content, pH, and temperature of the reaction solution. 1 In particular, pH (a measure of [H + ]) strongly determines the lifetimes of α-HHs derived from αterpineol (α-Tp) and terpinen-4-ol in aqueous phases. We found that not only these α-HHs but also α-alkoxyalkyl hydroperoxides possessing a −OOH group and a −OR' group generated from the reaction of α-Tp CIs with C 1 −C 3 alcohols decompose via an H + -catalyzed mechanism in aqueous phases.…”

Section: Introductionmentioning

confidence: 99%

“…11 It is important to note that atmospheric condensed phases are acidic by nature, 12 and H + -catalyzed reactions can therefore be expected to play essential roles in the fate of terpene-derived α-HHs and α-alkoxyalkyl hydroperoxides. 1 Whether the reactions of α-HHs with coreactants can compete with H + -catalyzed reactions has not been explored. Metal ions such as Fe 2+ , Zn 2+ , Cu 2+ , and Fe 3+ are ubiquitous in atmospheric condensed phases; and Fe 2+ and Fe 3+ , which are water-soluble, are known to play central roles in many atmospheric, environmental, and biological processes.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, multiphase ozonolysis of alkenes in the presence of water also produces α-HHs as major products. − Because of the hydrophilicity and large Henry’s law constants of α-HHs (e.g., the constant for hydroxymethyl-hydroperoxide is 5.0 × 10 5 M atm –1 at 295 K), these compounds are expected to reside mostly in condensed phases such as fog/cloud droplets, aqueous aerosols, and SOAs in the atmosphere. Recent studies revealed that liquid-phase α-HHs decompose to the corresponding aldehydes and H 2 O 2 at a rate that depends sensitively on the water content, pH, and temperature of the reaction solution . In particular, pH (a measure of [H + ]) strongly determines the lifetimes of α-HHs derived from α-terpineol (α-Tp) and terpinen-4-ol in aqueous phases.…”

Section: Introductionmentioning

confidence: 99%

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Effects of Metal Ions on Aqueous-Phase Decomposition of α-Hydroxyalkyl-Hydroperoxides Derived from Terpene Alcohols

Tonokura

Morino

et al. 2021

Environ. Sci. Technol.

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We report the results of a mass spectrometric study of the effects of atmospherically relevant metal ions on the decomposition of αhydroxyalkyl-hydroperoxides (α-HHs) derived from ozonolysis of α-terpineol in aqueous solutions. By direct mass spectrometric detection of chloride adducts of α-HHs, we assessed the temporal profiles of α-HHs and other products in the presence of metal ions. In addition, reactions between α-HHs and FeCl 2 in the presence of excess DMSO showed that the amount of hydroxyl radicals formed in a mixture of α-terpineol, O 3 , and FeCl 2 was 5.7 ± 0.8% of the amount formed in a mixture of H 2 O 2 and FeCl 2 . The first-order rate constants for the decay of α-HHs produced by ozonolysis of α-terpineol in the presence of 5 mM acetate buffer at a pH of 5.1 ± 0.1 were determined to be (4.5 ± 0.1) × 10 −4 s −1 (no metal ions), (4.7 ± 0.2) × 10 −4 s −1 (with 0.05 mM Fe 2+ ), (4.7 ± 0.1) × 10 −4 s −1 (with 0.05 mM Zn 2+ ), and (4.8 ± 0.2) × 10 −4 s −1 (with 0.05 mM Cu 2+ ). We propose that in acidic aqueous media, the reaction of α-HHs with Fe 2+ is outcompeted by H + -catalyzed decomposition of α-HHs, which produces the corresponding aldehydes and H 2 O 2 , which can in turn react with Fe 2+ to form hydroxyl radicals.

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