Preparation of β-caryophyllene oxidation products and their determination in ambient aerosol samples

Parshintsev, Jevgeni; Nurmi, Joonas; Kilpeläinen, Ilkka; Hartonen, Kari; Kulmala, Markku; Riekkola, Marja‐Liisa

doi:10.1007/s00216-007-1755-4

Cited by 51 publications

(41 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The relative contribution of α-pinene oxidation products to SOA formation has been predicted to be on the order of 20% (Andersson-Sköld et al, 2001). The significance of aldehydes in oxidation of sesquiterpenes, and especially their stability and presence in aerosol samples are confirmed by our most recent results (Parshintsev et al, 2008) It should be noted, however, that pinonaldehyde has a relatively high vapor pressure, and its presence in high concentrations in the aerosol is difficult to explain without invoking some degree of chemical bonding. It is possible that gasphase pinonaldehyde can adsorp onto quartz filters or absorb in the aerosol collected on the filters during the sampling.…”

Section: Aerosol Chemistry Following Nucleation Eventssupporting

confidence: 64%

The role of VOC oxidation products in continental new particle formation

et al. 2008

View full text Add to dashboard Cite

Abstract. Aerosol physical and chemical properties and trace gas concentrations were measured during the QUEST field campaign in March-April 2003, in Hyytiälä, Finland. Our aim was to understand the role of oxidation products of VOC's such as mono-and sesquiterpenes in atmospheric nucleation events. Particle chemical compositions were measured using the Aerodyne Aerosol Mass Spectrometer, and chemical compositions of aerosol samples collected with low-pressure impactors and a high volume sampler were analysed using a number of techniques. The results indicate that during and after new particle formation, all parti-cles larger than 50 nm in diameter contained similar organic substances that are likely to be mono-and sesquiterpene oxidation products. The oxidation products identified in the high volume samples were shown to be mostly aldehydes. In order to study the composition of particles in the 10-50 nm range, we made use of Tandem Differential Mobility Analyzer results. We found that during nucleation events, both 10 and 50 nm particle growth factors due to uptake of ethanol vapour correlate strongly with gas-phase monoterpene oxidation product (MTOP) concentrations, indicating that the organic constituents of particles smaller than 50 nm in diameter are at least partly similar to those of larger particles. We furthermore showed that particle growth rates during the nucleation events are correlated with the gas-phase MTOP Published by Copernicus Publications on behalf of the European Geosciences Union. 2658A. Laaksonen et al.: VOC oxidation products and new particle formation concentrations. This indicates that VOC oxidation products may have a key role in determining the spatial and temporal features of the nucleation events. This conclusion was supported by our aircraft measurements of new 3-10 nm particle concentrations, which showed that the nucleation event on 28 March 2003, started at the ground layer, i.e. near the VOC source, and evolved together with the mixed layer. Furthermore, no new particle formation was detected upwind away from the forest, above the frozen Gulf of Bothnia.

show abstract

Section: Aerosol Chemistry Following Nucleation Eventssupporting

confidence: 64%

The role of VOC oxidation products in continental new particle formation

et al. 2008

View full text Add to dashboard Cite

show abstract

“…The presence of common organic species in the aerosol particles has been corroborated in a number of observations [16][17][18][19][20][21][22][23] However, the role of organics in the atmospheric nucleation has long been underestimated or neglected due to the complexity of laboratory experiments and the absence of theoretical instruments, which would be able to account for the complex intermolecular interactions occurring in nucleating vapours. The importance of organic species has been pointed out in the pioneering experiments of Zhang et al [15], in which a considerable enhancement in nucleation rates due to organic species has been observed.…”

Section: Introductionmentioning

confidence: 94%

Amines in the Earth’s Atmosphere: A Density Functional Theory Study of the Thermochemistry of Pre-Nucleation Clusters

Nadykto

Jakovleva

et al. 2011

Entropy

166

174

View full text Add to dashboard Cite

The impact of organic species which are present in the Earth's atmosphere on the burst of new particles is critically important for the understanding of the molecular nature of atmospheric nucleation phenomena. Amines have recently been proposed as possible stabilizers of binary pre-nucleation clusters. In order to advance the understanding of atmospheric nucleation phenomena, a quantum-chemical study of hydrogen-bonded complexes of binary sulfuric acid-water clusters with methyl-, dimethyl-and trimethylamines representing common atmospheric organic species, vegetation products and laboratory impurities has been carried out. The thermochemical stability of the sulfuric acid-amines-water complexes was found to be higher than that of the sulfuric acid-ammonia-water complexes, in qualitative agreement with the previous studies. However, the enhancement in stability due to amines appears to not be large enough to overcome the difference in typical atmospheric concentrations of ammonia and amines. Further research is needed in order to address the existing uncertainties and to reach a final conclusion about the importance of amines for the atmospheric nucleation.

show abstract

“…β-caryophyllene has received particular attention, being one of the most reactive and abundant sesquiterpenes, and SOA yields have been reported in a number of ozonolysis and photo-oxidation studies (Hoffmann et al, 1997;Griffin et al, 1999;Jaoui et al, 2003;Lee et al 2006a, b;Winterhalter et al, 2009;Alfarra et al, 2012). As a result, its atmospheric degradation has been the subject of a number of experimental and theoretical mechanistic appraisals (Calogirou et al, 1997;Jaoui et al, 2003;Lee et al, 2006b;Kanawati et al, 2008;Winterhalter et al, 2009;Nguyen et al, 2009;Zhao et al, 2010;Li et al, 2011;Chan et al, 2011), and several established oxidation products have been used in tracer studies to show that β-caryophyllene-derived SOA makes potentially important contributions to ambient fine particulate matter at a number of locations Parshintsev et al 2008).…”

Section: Introductionmentioning

confidence: 99%

Development and chamber evaluation of the MCM v3.2 degradation scheme for β-caryophyllene

Jenkin¹,

et al. 2012

View full text Add to dashboard Cite

Abstract.A degradation mechanism for β-caryophyllene has recently been released as part of version 3.2 of the Master Chemical Mechanism (MCM v3.2), describing the gas phase oxidation initiated by reaction with ozone, OH radicals and NO 3 radicals. A detailed overview of the construction methodology is given, within the context of reported experimental and theoretical mechanistic appraisals. The performance of the mechanism has been evaluated in chamber simulations in which the gas phase chemistry was coupled to a representation of the gas-to-aerosol partitioning of 280 multi-functional oxidation products. This evaluation exercise considered data from a number of chamber studies of either the ozonolysis of β-caryophyllene, or the photo-oxidation of β-caryophyllene/NO x mixtures, in which detailed product distributions have been reported. This includes the results of a series of photo-oxidation experiments performed in the University of Manchester aerosol chamber, also reported here, in which a comprehensive characterization of the temporal evolution of the organic product distribution in the gas phase was carried out, using Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS), in conjunction with measurements of NO x , O 3 and SOA mass loading. The CIR-TOF-MS measurements allowed approximately 45 time-resolved product ion signals to be detected, which were assigned on the basis of the simulated temporal profiles of the more abundant MCM v3.2 species, and their probable fragmentation patterns. The evaluation studies demonstrate that the MCM v3.2 mechanism provides an acceptable description of β-caryophyllene degradation under the chamber conditions considered, with the temporal evolution of the observables identified above generally being recreated within the uncertainty bounds of key parameters within the mechanism. The studies have highlighted a number of areas of uncertainty or discrepancy, where further investigation would be valuable to help interpret the results of chamber studies and improve detailed mechanistic understanding. These particularly include: (i) quantification of the yield and stability of the secondary ozonide (denoted BCSOZ in MCM v3.2), formed from β-caryophyllene ozonolysis, and elucidation of the details of its further oxidation, including whether the products retain the "ozonide" functionality; (ii) investigation of the impact of NO x on the β-caryophyllene ozonolysis mechanism, in particular its effect on the formation of β-caryophyllinic acid (denoted Published by Copernicus Publications on behalf of the European Geosciences Union. M. E. Jenkin et al.: Development and chamber evaluation of the MCM v3.2 degradation schemeC137CO2H in MCM v3.2), and elucidation of its formation mechanism; (iii) routine independent identification of β-caryophyllinic acid, and its potentially significant isomer β-nocaryophyllonic acid (denoted C131CO2H in MCM v3.2); (iv) more precise quantification of the primary yield of OH (and other radicals) from β-caryophyllene ozonolysis; (v) quan...

show abstract

Preparation of β-caryophyllene oxidation products and their determination in ambient aerosol samples

Cited by 51 publications

References 24 publications

The role of VOC oxidation products in continental new particle formation

The role of VOC oxidation products in continental new particle formation

Amines in the Earth’s Atmosphere: A Density Functional Theory Study of the Thermochemistry of Pre-Nucleation Clusters

Development and chamber evaluation of the MCM v3.2 degradation scheme for β-caryophyllene

Contact Info

Product

Resources

About