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

Frege, Carla; Ortega, Ismael K.; Rissanen, Matti; Praplan, Arnaud P.; Steiner, Gerhard; Heinritzi, Martin; Ahonen, Lauri; Amorim, A.; Bernhammer, Anne-Kathrin; Bianchi, Federico; Brilke, Sophia; Breitenlechner, Martin; Dada, Lubna; Dias, António; Duplissy, Jonathan; Ehrhart, Sebastian; Haddad, Imad El; Fischer, Lukas; Fuchs, Claudia; Garmаsh, Olga; Gonin, Marc; Hansel, Armin; Hoyle, C. R.; Jokinen, Tuija; Junninen, Heikki; Kirkby, J.; Kürten, Andreas; Lehtipalo, Katrianne; Leiminger, Markus; Mauldin, R. L.; Molteni, Ugo; Nichman, Leonid; Petäj̈ä, Tuukka; Sarnela, Nina; Schobesberger, Siegfried; Simon, Mario; Sipilä, Mikko; Stolzenburg, Dominik; Tomé, António; Vogel, Alexander L.; Wagner, Andrea C.; Wagner, R. J.; Xiao, Mao; Yan, Chao; Ye, Penglin; Curtius, Joachim; Donahue, Neil M.; Flagan, R. C.; Kulmala, Markku; Worsnop, Douglas R.; Winkler, Paul M.; Dommen, Josef; Baltensperger, Urs

doi:10.5194/acp-2017-426

Cited by 12 publications

(25 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is similar to the observations in ref. 15 , where a significant decrease in O:C of the nucleating charged clusters was observed at colder temperatures.…”

Section: Resultsmentioning

confidence: 96%

“…Therefore, temperature likely plays a decisive role, as the saturation concentration has a steep exponential temperature dependence as described by the Clausius–Clapeyron relation. Additionally, a recent study has shown that temperature crucially influences the chemical composition of the initially formed molecular clusters in

-pinene ozonolysis ( 15 ). Therefore, the contribution of biogenic organics to new particle formation might be strongly sensitive to temperature.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range

Stolzenburg

Fischer

Vogel

et al. 2018

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

Self Cite

152

191

View full text Add to dashboard Cite

SignificanceAerosol particles can form and grow by gas-to-particle conversion and eventually act as seeds for cloud droplets, influencing global climate. Volatile organic compounds emitted from plants are oxidized in the atmosphere, and the resulting products drive particle growth. We measure particle growth by oxidized biogenic vapors with a well-controlled laboratory setup over a wide range of tropospheric temperatures. While higher temperatures lead to increased reaction rates and concentrations of highly oxidized molecules, lower temperatures allow additional, but less oxidized, species to condense. We measure rapid growth over the full temperature range of our study, indicating that organics play an important role in aerosol growth throughout the troposphere. Our finding will help to sharpen the predictions of global aerosol models.

show abstract

“…This is similar to the observations in ref. 15 , where a significant decrease in O:C of the nucleating charged clusters was observed at colder temperatures.…”

Section: Resultsmentioning

confidence: 96%

-pinene ozonolysis ( 15 ). Therefore, the contribution of biogenic organics to new particle formation might be strongly sensitive to temperature.…”

mentioning

confidence: 99%

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range

Stolzenburg

Fischer

Vogel

et al. 2018

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

Self Cite

152

191

View full text Add to dashboard Cite

show abstract

“…At low temperatures, all HOM species have reduced volatility and thus a larger fraction can participate in particle nucleation and growth -although this is partially compensated for by the slower production rate of HOMs. Temperature also affects the composition and stability of formed HOM clusters (Frege et al, 2017). As a result, the neutral fraction at a given MT concentration is higher at lower temperatures ( Fig.…”

Section: Fraction Of Neutral Particle Formation In Different Chemicalmentioning

confidence: 99%

The role of ions in new particle formation in the CLOUD chamber

et al. 2017

Self Cite

View full text Add to dashboard Cite

Abstract. The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nanoparticle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e., in conditions in which neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.5 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion-ion recombination before they grew to 2.5 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.5 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.

show abstract

“…The impact of decreased HOM on new-particle growth rates was compensated by less oxidized species being able to condense at the lower temperatures. In another study, Frege et al (2018) also concluded that HOM formation decreased at lower temperatures, but their study was based on observations of naturally charged ions using an APi-TOF, complicating the interpretation of HOM formation rates.…”

Section: Introductionmentioning

confidence: 99%

Effect of temperature on the formation of Highly-oxygenated Organic Molecules (HOM) from alpha-pinene ozonolysis

Quéléver¹,

Kristensen²,

Jensen³

et al. 2018

Preprint

View full text Add to dashboard Cite

Abstract. Highly-oxygenated Organic Molecules (HOM) are important contributors to Secondary Organic Aerosol (SOA) and New-Particle Formation (NPF) in the boreal atmosphere. This newly discovered class of molecules is efficiently formed from atmospheric oxidation of biogenic volatile organic compounds (VOC), such as monoterpenes, through a process called autoxidation. This process, in which peroxy-radical intermediates isomerize to allow addition of molecular oxygen, is expected to be highly temperature-dependent. Here, we studied the dynamics of HOM formation during alpha-pinene ozonolysis experiments performed at three different temperatures, 20&#8201;&#176;C, 0&#8201;&#176;C and &#8722;15&#8201;&#176;C, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50&#8201;ppb alpha-pinene, 100&#8201;ppb ozone), decreased considerably as temperature decreased, with molar yields dropping by around a factor of 50 when experiments were performed at 0&#8201;&#176;C, compared to 20&#8201;&#176;C. At &#8722;15&#8201;&#176;C, the HOM signals were already close to the detection limit of the nitrate-based Chemical Ionization Atmospheric Pressure interface Time Of Flight (CI-APi-TOF) mass spectrometer used for measuring gas-phase HOM. Surprisingly, very little difference was seen in the mass spectral distribution of the HOM molecules of interest at 0&#8201;&#176;C and 20&#8201;&#176;C, with e.g. the ratios between the typical HOM products C10H14O7, C10H14O9, and C10H14O11 remaining fairly constant. The more oxidized species have undergone more isomerization steps, yet, at lower temperature, they did not decrease more than the less oxidized species. One possible explanation is be that the rate-limiting step forming these HOM occurs before the products become oxygenated enough to be detected by our CI-APi-TOF (i.e. typically seven or more oxygen atoms). The strong temperature dependence of HOM formation was observed under temperatures highly relevant for the boreal forest, but the exact magnitude of this effect in the atmosphere will be much more complex: the fate of peroxy-radicals is a competition between autoxidation (influenced by temperature and VOC type) and bimolecular termination pathways (influenced mainly by concentration of reaction partners). While the temperature influence is likely smaller in the boreal atmosphere than in our chamber, the magnitude and complexity of this effect clearly deserves more consideration in future studies in order to estimate the ultimate role of HOM on SOA and NPF under different atmospheric conditions.

show abstract

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

Cited by 12 publications

References 0 publications

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range

The role of ions in new particle formation in the CLOUD chamber

Effect of temperature on the formation of Highly-oxygenated Organic Molecules (HOM) from alpha-pinene ozonolysis

Contact Info

Product

Resources

About