Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone

Glasius, Marianne; Lahaniati, M.; Calogirou, A.; Bella, Dario Di; Jensen, N. R.; Hjorth, J.; Kotzias, D.; Larsen, B.

doi:10.1021/es990445r

Cited by 309 publications

(338 citation statements)

References 45 publications

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“…In the α-and β-pinene schemes, the following isomerisation reactions are included in competition with alternative decomposition routes: These reactions were included to allow the formation of the identified products pinic acid from α-and β-pinene degradation and 10-hydroxypinonic acid from α-pinene degradation (e.g. Christoffersen et al, 1998;Hoffmann et al, 1998;Jang and Kamens, 1999;Glasius et al, 2000), as described by . Reaction (25) for the complex acyl-oxy radical is assigned a probability of 80%, with the remaining 20% decomposing to eliminate CO 2 and an organic radical (in accordance with the reaction assumed for acyl-oxy radicals in general).…”

Section: Reactions Of Oxy Radical Intermediatesmentioning

confidence: 99%

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

et al. 2003

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Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g., α-and β-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the α-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in α-pinene/NO X photo-oxidation experiments carried out in the European Photoreactor (EU-PHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM.

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Section: Reactions Of Oxy Radical Intermediatesmentioning

confidence: 99%

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

et al. 2003

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“…In this context, a recent study by Zhang et al (2017) provided evidence for the formation of 7-hydroperoxypinonic acid from degradation of an unstable dimer precursor in α-pinene/O 3 SOA. It is also worth mentioning that both cis-pinic acid (e.g., Yu et al, 1999;Glasius et al, 2000;Larsen et al, 2001;Winterhalter et al, 2003) and 7-hydroxypinonic acid (e.g., Glasius et al, 1999;Larsen et al, 2001;Yasmeen et al, 2012) are known to be present in α-pinene/O 3 SOA. The proposed mechanism is consistent with the observation made by Zhang et al (2015) that cis-pinic acid is still generated after consumption of α-pinene upon ozonolysis, suggesting a particle-phase production pathway.…”

Section: Formation Mechanism Proposed For the Mw 368 Estermentioning

confidence: 99%

High-molecular-weight esters in <i>α</i>-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules

et al. 2018

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Abstract. Stable high-molecular-weight esters are present in α-pinene ozonolysis secondary organic aerosol (SOA) with the two most abundant ones corresponding to a hydroxypinonyl ester of cis-pinic acid with a molecular weight (MW) of 368 (C 19 H 28 O 7 ) and a diaterpenylic ester of cis-pinic acid with a MW of 358 (C 17 H 26 O 8 ). However, their molecular structures are not completely elucidated and their relationship with highly oxygenated molecules (HOMs) in the gas phase is still unclear. In this study, liquid chromatography in combination with positive ion electrospray ionization mass spectrometry has been performed on highmolecular-weight esters present in α-pinene ozonolysis SOA with and without derivatization into methyl esters. Unambiguous evidence could be obtained for the molecular structure of the MW 368 ester in that it corresponds to an ester of cis-pinic acid where the carboxyl substituent of the dimethylcyclobutane ring and not the methylcarboxyl substituent is esterified with 7-hydroxypinonic acid. The same linkage was already proposed in previous work for the MW 358 ester (Yasmeen et al., 2010), but could be supported in the present study. Guided by the molecular structures of these stable esters, we propose a formation mechanism from gas-phase HOMs that takes into account the formation of an unstable C 19 H 28 O 11 product, which is detected as a major species in α-pinene ozonolysis experiments as well as in the pristine forest atmosphere by chemical ionization-atmospheric pressure ionization-time-of-flight mass spectrometry with nitrate clustering (Ehn et al., 2012. It is suggested that an acyl peroxy radical related to cis-pinic acid (RO 2 q ) and an alkoxy radical related to 7-or 5-hydroxypinonic acid (R O q ) serve as key gas-phase radicals and combine according to a RO 2 + R O q → RO 3 R radical termination reaction. Subsequently, the unstable C 19 H 28 O 11 HOM species decompose through the loss of oxygen or ketene from the inner part containing a labile trioxide function and the conversion of the unstable acyl hydroperoxide groups to carboxyl groups, resulting in stable esters with a molecular composition of C 19 H 28 O 7 (MW 368) and C 17 H 26 O 8 (MW 358), respectively. The proposed mechanism is supported by several observations reported in the literature. On the basis of the indirect evidence presented in this study, we hypothesize that RO 2 + R O q → RO 3 R chemistry is at the underlying molecular basis of high-molecular-weight ester formation upon α-pinene ozonolysis and may thus be of importance for new particle formation and growth in pristine forested environments.

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“…Oxalic acid (C 2 ) is usually the dominant organic species in aerosols (Kawamura and Sakaguchi, 1999). Diacids are emitted primarily from combustion of fossil fuels, i.e., motor exhausts and coal burning, and biomass burning (Graham et al, 2002;Kawamura and Kaplan, 1987;Kundu et al, 2010a, b;Narukawa et al, 1999), but more importantly produced by the secondary oxidation of anthropogenic and biogenic volatile organic compounds (VOCs) in the atmosphere (Glasius et al, 2000;Kawamura et al, 1996a;Legrand et al, 2007). Aqueous-phase production of C 2 is also important in aerosol/cloud/fog droplets (Warneck, 2003).…”

Section: Introductionmentioning

confidence: 99%

Diurnal and temporal variations of water-soluble dicarboxylic acids and related compounds in aerosols from the northern vicinity of Beijing: Implication for photochemical aging during atmospheric transport

He¹,

Kawamura²,

Okuzawa³

et al. 2014

Science of The Total Environment

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Abstract:Aerosol samples were collected in autumn 2007 on day-and nighttime basis in the northern receptor site of Beijing, China. The samples were analyzed for total carbon (TC) and water-soluble dicarboxylic acids (C 2 -C 12 ), oxocarboxylic acids (C 2 -C 9 ), glyoxal and methylglyoxal to better understand the photochemical aging of organic aerosols in the vicinity of Beijing. Concentrations of TC are 50% greater in daytime when winds come from Beijing than in nighttime when winds come from the northern forest areas. Most diacids showed higher concentrations in daytime, suggesting that the organics emitted from the urban Beijing and delivered to the northern vicinity in daytime are subjected to photo-oxidation to result in diacids.However, oxalic acid (C 2 ), which is the most abundant diacid followed by C 3 or C 4 , became on average 30% more abundant in nighttime together with azelaic, ω-oxooctanoic and ω-oxononanoic acids, which are specific oxidation products of biogenic unsaturated fatty acids.Methylglyoxal, an oxidation product of isoprene and a precursor of oxalic acid, also became 29% more abundant in nighttime. Based on a positive correlation between C 2 and glyoxylic acid (ωC 2 ) in nighttime when relative humidity significantly enhanced, we propose a nighttime aqueous phase production of C 2 via the oxidation of ωC 2 . We found an increase in the contribution of diacids to TC by 3 folds during consecutive clear days. This study demonstrates that diacids and related compounds are largely produced in the northern vicinity of Beijing via photochemical processing of organic precursors emitted from urban center and forest areas.

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Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone

Cited by 309 publications

References 45 publications

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

High-molecular-weight esters in <i>α</i>-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules

Diurnal and temporal variations of water-soluble dicarboxylic acids and related compounds in aerosols from the northern vicinity of Beijing: Implication for photochemical aging during atmospheric transport

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Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone

Cited by 309 publications

References 45 publications

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

High-molecular-weight esters in &lt;i&gt;α&lt;/i&gt;-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules

Diurnal and temporal variations of water-soluble dicarboxylic acids and related compounds in aerosols from the northern vicinity of Beijing: Implication for photochemical aging during atmospheric transport

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High-molecular-weight esters in <i>α</i>-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules