Development and application of a possible mechanism for the generation of cis-pinic acid from the ozonolysis of α- and β-pinene

Jenkin, Michael E.; Shallcross, Dudley E.; Harvey, Jeremy N.

doi:10.1016/s1352-2310(00)00087-x

Cited by 162 publications

(204 citation statements)

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“…This demonstrates that traditionally cited particlephase esterification is not important in dimer production. It is also consistent with the general α-pinene degradation chemistry in the gas phase, where the diacyl peroxide precursors, acetylperoxy radicals, are one of the major products from the ozonolysis vinylhydroperoxide channel, but rather limited from the OH oxidation pathway (6). Additionally, the mass fraction of the ELVOC dimers decreases significantly as the ozonolysis reaction proceeds (Fig.…”

Section: Resultssupporting

confidence: 86%

Formation and evolution of molecular products in α-pinene secondary organic aerosol

Zhang

McVay

Huang

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

253

401

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Much of our understanding of atmospheric secondary organic aerosol (SOA) formation from volatile organic compounds derives from laboratory chamber measurements, including mass yield and elemental composition. These measurements alone are insufficient to identify the chemical mechanisms of SOA production. We present here a comprehensive dataset on the molecular identity, abundance, and kinetics of α-pinene SOA, a canonical system that has received much attention owing to its importance as an organic aerosol source in the pristine atmosphere. Identified organic species account for ∼58-72% of the α-pinene SOA mass, and are characterized as semivolatile/low-volatility monomers and extremely low volatility dimers, which exhibit comparable oxidation states yet different functionalities. Features of the α-pinene SOA formation process are revealed for the first time, to our knowledge, from the dynamics of individual particle-phase components. Although monomeric products dominate the overall aerosol mass, rapid production of dimers plays a key role in initiating particle growth. Continuous production of monomers is observed after the parent α-pinene is consumed, which cannot be explained solely by gasphase photochemical production. Additionally, distinct responses of monomers and dimers to α-pinene oxidation by ozone vs. hydroxyl radicals, temperature, and relative humidity are observed. Gas-phase radical combination reactions together with condensed phase rearrangement of labile molecules potentially explain the newly characterized SOA features, thereby opening up further avenues for understanding formation and evolution mechanisms of α-pinene SOA.secondary organic aerosol | particulate matter | air quality | climate S econdary organic aerosol (SOA), comprising a large number of structurally different organic oxygenates, is a dominant constituent of submicrometer atmospheric particulate matter (1). Molecular characterization of SOA has been a major research goal in atmospheric chemistry for several decades (2), owing to the importance of organic aerosol in air quality and Earth's energy budget. Both biogenic (e.g., isoprene, monoterpenes) and anthropogenic (e.g., aromatics, large alkanes) organic compounds are well-established precursors to SOA. Knowledge of the SOA molecular composition is crucial for elucidation of its underlying formation mechanisms.The most abundant monoterpene in the troposphere is α-pinene (3). The oxidation of α-pinene by ozone has become a canonical SOA system (4-12). Identification of multifunctional particlephase products has been reported, including monomers with carboxylic acid moieties (4, 6) and high-molecular-weight compounds (7,8,12), although molecular structures and formation pathways of oligomers remain uncertain (5). Recently, a class of extremely low-volatility gas-phase organic compounds (ELVOCs) has been identified as an important component in the α-pinene ozonolysis chemistry (13). Identification of the ELVOCs in the particle phase and elucidation of the mechanism of their format...

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Section: Resultssupporting

confidence: 86%

Formation and evolution of molecular products in α-pinene secondary organic aerosol

Zhang

McVay

Huang

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

253

401

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“…Keywood et al (2004) explained this behaviour by the involvement of acylperoxyradicals formed via isomerisation of alkoxy radical which in turn are produced from Crieege Intermediates during ozonolysis of endocyclic alkenes. Winterhalter et al (2000), Koch et al (2000) and Jenkin et al (2000) showed that acylperoxy radicals from both endo-and exocyclic monoterpenes are involved in the formation of dicarboxylic acids via permutation reactions with HO 2 or RO 2 radicals. These radical reactions are initiated by the decomposition of the excited Criegee Intermediates via the hydroperoxy channel or the ester channel (Calvert et al, 2000).…”

Section: Chemistry Of Secondary Organic Aerosol Formationmentioning

confidence: 99%

Organic aerosol and global climate modelling: a review

et al. 2005

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Abstract. The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies.

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“…There are three features of note. First, the well-characterized products from this reaction, such as norpinone aldehyde (MW=154), terpenylic acid (MW=172) and cis-pinic acid (MW=186) (Jenkin et al, 2000;Larsen et al, 2001;Claeys et al, 2009) …”

Section: Identification Of Rooh In Soa Materials 30mentioning

confidence: 99%

Identification of Organic Hydroperoxides and Peroxy Acids Using Atmospheric Pressure Chemical Ionization – Tandem Mass Spectrometry (APCI-MS/MS): Application to Secondary Organic Aerosol

Zhou¹,

Rivera-Rios²,

Keutsch³

et al. 2018

Preprint

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Abstract.Molecules with hydroperoxide functional groups are of extreme importance to both the atmospheric and biological 10 chemistry fields. In this work, an analytical method is presented for the identification of organic hydroperoxides and peroxy and peracetic acid), as well as the ROOH formed from the reactions of H 2 O 2 with aldehydes (i.e. acetaldehyde, hexanal, glyoxal and methylglyoxal). This new ROOH detection method was applied to methanol extracts of secondary organic aerosol (SOA) material generated from ozonolysis of α-pinene, indicating a number of ROOH molecules in the SOA material. While the full scan mass spectrum of SOA demonstrates the presence of monomers (m/z=80-250), dimers (m/z=250-450) and trimers (m/z=450-600), the neutral loss scan shows that the ROOH products all have masses less than 20 300 Da, indicating that ROOH molecules may not contribute significantly to the SOA oligomeric content. We anticipate this method could also be applied to biological systems with considerable value.

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Development and application of a possible mechanism for the generation of cis-pinic acid from the ozonolysis of α- and β-pinene

Cited by 162 publications

References 50 publications

Formation and evolution of molecular products in α-pinene secondary organic aerosol

Formation and evolution of molecular products in α-pinene secondary organic aerosol

Organic aerosol and global climate modelling: a review

Identification of Organic Hydroperoxides and Peroxy Acids Using Atmospheric Pressure Chemical Ionization – Tandem Mass Spectrometry (APCI-MS/MS): Application to Secondary Organic Aerosol

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