Newly observed peroxides and the water effect on the formation and removal of hydroxyalkyl hydroperoxides in the ozonolysis of isoprene

Abstract. The ozonolysis of alkenes is considered to be an important source of atmospheric peroxides, which serve as oxidants, reservoirs of HOx radicals, and components of secondary organic aerosols (SOAs). Recent laboratory investigations of this reaction identified hydrogen peroxide (H2O2) and hydroxymethyl hydroperoxide (HMHP) in ozonolysis of isoprene. Although larger hydroxyalkyl hydroperoxides (HAHPs) were also expected, their presence is not currently supported by experimental evidence. In the present study, we investigated the formation of peroxides in the gas phase ozonolysis of isoprene at various relative humidities on a time scale of tens of seconds, using a quartz flow tube reactor coupled with the online detection of peroxides. We detected a variety of conventional peroxides, including H2O2, HMHP, methyl hydroperoxide, bis-hydroxymethyl hydroperoxide, and ethyl hydroperoxide, and interestingly found three unknown peroxides. The molar yields of the conventional peroxides fell within the range of values provided in the literature. The three unknown peroxides had a combined molar yield of ~ 30% at 5% relative humidity (RH), which was comparable with that of the conventional peroxides. Unlike H2O2 and HMHP, the molar yields of these three unknown peroxides were inversely related to the RH. On the basis of experimental kinetic and box model analysis, we tentatively assigned these unknown peroxides to C2−C4 HAHPs, which are produced by the reactions of different Criegee intermediates with water. Our study provides experimental evidence for the formation of large HAHPs in the ozonolysis of isoprene (one of the alkenes). These large HAHPs have a sufficiently long lifetime, estimated as tens of minutes, which allows them to become involved in atmospheric chemical processes, e.g., SOA formation and radical recycling.

• Publication year

  2013

• Venue

  Atmospheric Chemistry and Physics

• Publication date

  2013-06-12

• Fields of study

  Chemistry, Environmental Science

• Identifiers
  DOI 10.5194/ACP-13-5671-2013
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar

• No claims are published for this paper.

• No concepts are published for this paper.

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• Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3.

  2005cited by this paper
• Secondary organic aerosol formation from isoprene photooxidation.

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• A theoretical study of the reactions of parent and substituted Criegee intermediates with water and the water dimer

  2004influential reference
• High contribution of biogenic hydroperoxides to secondary organic aerosol formation

  2004cited by this paper
• Atmospheric degradation of volatile organic compounds.

  2003cited by this paper
• Reaction of Criegee Intermediates with Water VaporAn Additional Source of OH Radicals in Alkene Ozonolysis

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• Theoretical studies on isoprene ozonolysis under tropospheric conditions. 1. Reaction of substituted carbonyl oxides with water

  2003influential reference
• Theoretical studies of the isoprene ozonolysis under tropospheric conditions. 2. Unimolecular and water-assisted decomposition of the α-hydroxy hydroperoxides

  2003influential reference
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  2002cited by this paper
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  2000cited by this paper
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  2000cited by this paper
• Formation of hydrogen peroxide in the ozonolysis of isoprene and simple alkenes under humid conditions

  1999influential reference
• Atmospheric Chemistry and Physics: From Air Pollution to Climate Change

  1998cited by this paper
• The tropospheric degradation of volatile organic compounds: a protocol for mechanism development

  1997cited by this paper
• Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour

  1997influential reference
• The reactions of ozone with alkenes: An important source of HOx in the boundary layer

  1996cited by this paper
• Formation of alkyl and hydroxyalkyl hydroperoxides on ozonolysis in water and in air

  1995influential reference
• HPLC Determination of Atmospheric Organic Hydroperoxides

  1995cited by this paper
• OH radical‐ initiated photooxidation of isoprene: An estimate of global CO production

  1994cited by this paper
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  1994cited by this paper
• Reactions of criegee intermediates in the gas phase

  1994influential reference
• Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes

  1992influential reference
• Formation and occurrence of organic hydroperoxides in the troposphere: Laboratory and field observations

  1991cited by this paper
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  1991influential reference
• Reactions of OH with α‐pinene and β‐pinene in air: Estimate of global CO production from the atmospheric oxidation of terpenes

  1991cited by this paper
• Production of hydrogen peroxide in forest air by reaction of ozone with terpenes

  1990cited by this paper
• Reaction of CH3O2+HO2 in air at 295 K: A product study

  1990influential reference
• Hydroperoxides in plants exposed to ozone mediate air pollution damage to alkene emitters

  1990cited by this paper
• Photodissociation of H2O2 and CH3OOH at 248 nm and 298 K: Quantum yields for OH, O(3P) and H(2S)

  1990influential reference
• Chemical mechanisms of acid generation in the troposphere

  1985cited by this paper
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  1985influential reference
• Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds

  year unknowncited by this paper

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