Elemental composition and clustering behaviour of α-pinene oxidation products for different oxidation conditions

Praplan, Arnaud P.; Schobesberger, Siegfried; Bianchi, Federico; Rissanen, Matti; Ehn, Mikael; Jokinen, Tuija; Junninen, Heikki; Adamov, Alexey; Amorim, A.; Dommen, Josef; Duplissy, Jonathan; Hakala, J.; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Kirkby, J.; Krapf, Manuel; Kürten, Andreas; Lehtipalo, Katrianne; Riccobono, Francesco; Rondo, Linda; Sarnela, Nina; Simon, Mario; Tomé, António; Tröstl, Jasmin; Winkler, Paul M.; Williamson, Christina; Ye, P.; Curtius, Joachim; Baltensperger, Urs; Donahue, Neil M.; Kulmala, Markku; Worsnop, Douglas R.

doi:10.5194/acp-15-4145-2015

Cited by 23 publications

(29 citation statements)

References 60 publications

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“…Although these techniques could provide the molecular formula of the compounds, the molecular structures are unknown. In order to derive further information, comparison to previous publications was performed for the major oxidation products from (a) the β-pinene ozonolysis (Chen and Griffin, 2005;Hohaus et al, 2015;Jenkin, 2004;Yu et al, 1999), (b) limonene ozonolysis and NO 3 oxidation (Chen and Griffin, 2005;Jaoui et al, 2006;Kundu et al, 2012;Leungsakul et al, 2005a, b) and (c) tree emissions ozonolysis, with α-pinene and 3 -carene being the major reactants (Chen and Griffin, 2005;Praplan et al, 2015;Yu et al, 1999). Results showed that all techniques were able to detect most of the expected molecules.…”

Section: Compound Detection Comparison and Tracer Attributionmentioning

confidence: 99%

Comparison of three aerosol chemical characterization techniques utilizing PTR-ToF-MS: a study on freshly formed and aged biogenic SOA

Gkatzelis¹,

Tillmann²,

Hohaus³

et al. 2018

Atmos. Meas. Tech.

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Abstract. An intercomparison of different aerosol chemical characterization techniques has been performed as part of a chamber study of biogenic secondary organic aerosol (BSOA) formation and aging at the atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). Three different aerosol sampling techniques -the aerosol collection module (ACM), the chemical analysis of aerosol online (CHARON) and the collection thermal-desorption unit (TD) were connected to proton transfer reaction time-of-flight mass spectrometers (PTR-ToF-MSs) to provide chemical characterization of the SOA. The techniques were compared among each other and to results from an aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS). The experiments investigated SOA formation from the ozonolysis of β-pinene, limonene, a β-pinene-limonene mix and real plant emissions from Pinus sylvestris L. (Scots pine). The SOA was subsequently aged by photo-oxidation, except for limonene SOA, which was aged by NO 3 oxidation. Despite significant differences in the aerosol collection and desorption methods of the PTR-based techniques, the determined chemical composition, i.e. the same major contributing signals, was found by all instruments for the different chemical systems studied. These signals could be attributed to known products expected from the oxidation of the examined monoterpenes. The sampling and desorption method of ACM and TD provided additional information on the volatility of individual compounds and showed relatively good agreement.Averaged over all experiments, the total aerosol mass recovery compared to an SMPS varied within 80 ± 10, 51 ± 5 and 27 ± 3 % for CHARON, ACM and TD, respectively. Comparison to the oxygen-to-carbon ratios (O : C) obtained by AMS showed that all PTR-based techniques observed lower O : C ratios, indicating a loss of molecular oxygen either during aerosol sampling or detection. The differences in total mass recovery and O : C between the three instruments resulted predominantly from differences in the field strength (E/N) in the drift tube reaction ionization chambers of the PTR-ToF-MS instruments and from dissimilarities in the collection/desorption of aerosols. Laboratory case studies showed that PTR-ToF-MS E/N conditions influenced fragmentation which resulted in water and further neutral fragment losses of the detected molecules. Since ACM and TD were operated in higher E/N than CHARON, this resulted in higher fragmentation, thus affecting primarily the detected oxygen and carbon content and therefore also the mass recovery. Overall, these techniques have been shown to provide

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Section: Compound Detection Comparison and Tracer Attributionmentioning

confidence: 99%

Comparison of three aerosol chemical characterization techniques utilizing PTR-ToF-MS: a study on freshly formed and aged biogenic SOA

Gkatzelis¹,

Tillmann²,

Hohaus³

et al. 2018

Atmos. Meas. Tech.

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“…The experiments were carried out with the CLOUD chamber at CERN, which has been described by Kirkby et al (2011), Almeida et al (2013) and Duplissy et al (2015). In brief, the CLOUD chamber is a cylindrical electropolished stainlesssteel tank with a volume of 26.1 m 3 .…”

Section: Cloud Chambermentioning

confidence: 99%

“…E and F). In these experiments, hydrogen (H 2 ) was added to suppress OH radicals from α-pinene ozonolysis in order to probe the role of ozonolysis alone on new particle formation (Praplan et al, 2015). Although the concentrations of sulfuric acid were higher during the sulfuric acid-organics experiments than during the sulfuric acid-dimethylamine experiments, the HGFs of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine, as can be seen in Table 1.…”

Section: The Role Of Dimethylamine-or α-Pinene-related Secondary Orgamentioning

confidence: 99%

Hygroscopicity of nanoparticles produced from homogeneous nucleation in the CLOUD experiments

et al. 2016

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Abstract. Sulfuric acid, amines and oxidized organics have been found to be important compounds in the nucleation and initial growth of atmospheric particles. Because of the challenges involved in determining the chemical composition of objects with very small mass, however, the properties of the freshly nucleated particles and the detailed pathways of their formation processes are still not clear. In this study, we focus on a challenging size range, i.e., particles that have grown to diameters of 10 and 15 nm following nucleation, and measure their water uptake. Water uptake is useful information for indirectly obtaining chemical composition of aerosol particles. We use a nanometer-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) at subsaturated conditions (ca. 90 % relative humidity at 293 K) toPublished by Copernicus Publications on behalf of the European Geosciences Union. J. Kim et al.: Hygroscopicity of nanoparticles produced from homogeneous nucleationmeasure the hygroscopicity of particles during the seventh Cosmics Leaving OUtdoor Droplets (CLOUD7) campaign performed at CERN in 2012. In CLOUD7, the hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid-dimethylamine, and sulfuric acid-organics derived from α-pinene oxidation. The hygroscopicity parameter κ decreased with increasing particle size, indicating decreasing acidity of particles. No clear effect of the sulfuric acid concentration on the hygroscopicity of 10 nm particles produced from sulfuric acid and dimethylamine was observed, whereas the hygroscopicity of 15 nm particles sharply decreased with decreasing sulfuric acid concentrations. In particular, when the concentration of sulfuric acid was 5.1 × 10 6 molecules cm −3 in the gas phase, and the dimethylamine mixing ratio was 11.8 ppt, the measured κ of 15 nm particles was 0.31 ± 0.01: close to the value reported for dimethylaminium sulfate (DMAS) (κ DMAS ∼ 0.28). Furthermore, the difference in κ between sulfuric acid and sulfuric acid-dimethylamine experiments increased with increasing particle size. The κ values of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine. This suggests that the organics produced from α-pinene ozonolysis play a significant role in particle growth even at 10 nm sizes.

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“…The (extremely) low volatility of the HOMs results in efficient NPF and growth, even in the absence of sulfuric acid . The chemical composition of HOMs during NPF has been identified from α-pinene and pinanediol oxidation by Praplan et al (2015) and Schobesberger et al (2013), respectively.…”

Section: Introductionmentioning

confidence: 99%

Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

et al. 2018

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Abstract. It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1-2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 • C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and −25 • C). Most negative HOM clusters include a nitrate (NO − 3 ) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH + 4 ) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ∼ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (−25 • C), the presence of C 30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.

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Elemental composition and clustering behaviour of α-pinene oxidation products for different oxidation conditions

Cited by 23 publications

References 60 publications

Comparison of three aerosol chemical characterization techniques utilizing PTR-ToF-MS: a study on freshly formed and aged biogenic SOA

Comparison of three aerosol chemical characterization techniques utilizing PTR-ToF-MS: a study on freshly formed and aged biogenic SOA

Hygroscopicity of nanoparticles produced from homogeneous nucleation in the CLOUD experiments

Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

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