Molecular Composition and Volatility of Nucleated Particles from α-Pinene Oxidation between −50 °C and +25 °C

Ye, Qing; Wang, Mingyi; Hofbauer, Victoria; Stolzenburg, Dominik; Chen, Dexian; Schervish, Meredith; Vogel, Alexander L.; Mauldin, R. L.; Baalbaki, Rima; Brilke, Sophia; Dada, Lubna; Dias, António; Duplissy, Jonathan; Haddad, Imad El; Finkenzeller, Henning; Fischer, Lukas; He, Xu‐Cheng; Kim, Changhyuk; Kürten, Andreas; Lamkaddam, Houssni; Lee, Chuan Ping; Lehtipalo, Katrianne; Leiminger, Markus; Manninen, Hanna E.; Marten, Ruby; Mentler, Bernhard; Partoll, Eva; Petäj̈ä, Tuukka; Rissanen, Matti; Schobesberger, Siegfried; Schuchmann, S.; Simon, Mario; Tham, Yee Jun; Vazquez‐Pufleau, Miguel; Wagner, Andrea C.; Wang, Yonghong; Wu, Yusheng; Xiao, Mao; Baltensperger, Urs; Curtius, Joachim; Flagan, Richard C.; Kirkby, J.; Kulmala, Markku; Volkamer, Rainer; Winkler, Paul M.; Worsnop, Douglas R.; Donahue, Neil M.

doi:10.1021/acs.est.9b03265

Cited by 46 publications

(47 citation statements)

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“…This is probably because of their very low concentrations and the difficulty to distinguish between real particle signal and background. We conjecture that especially at low temperatures this issue might be related to the fact that at lower temperatures, the autoxidation process to form HOMs is slower; therefore, the oxygen content and O : C decrease (Stolzenburg et al, 2018;Ye et al, 2019;Simon et al, 2020). The low contribution of these compounds in the gas phase might be reflected in the particle phase.…”

Section: Influence Of Relative Humidity On α-Pinene System At −50 • Cmentioning

confidence: 96%

“…For instance, Kristensen et al (2017), measuring at −15 and +20 • C, showed an increased contribution of less oxygenated species to α-pinene SOA particles formed from ozonolysis at sub-zero temperatures. Ye et al (2019) measured the particle-phase chemical composition from α-pinene oxidation between −50 and +25 • C with the FIGAERO inlet (Lopez-Hilfiker et al, 2014). They found that during new particle formation from α-pinene oxidation, gas-phase chemistry directly determines the composition of the condensed phase.…”

Section: Introductionmentioning

confidence: 99%

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Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

et al. 2021

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Abstract. Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

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Section: Influence Of Relative Humidity On α-Pinene System At −50 • Cmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

et al. 2021

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“…S1); otherwise, the nitrate ionization scheme cannot fully detect them. The unimolecular reaction of the RO q 2 radicals proceeds at much slower rates at low temperatures, due to the height of the reaction barrier, while the bimolecular termination of the radicals is much less affected by the temperature (Ziemann and Atkinson, 2012;Frege et al, 2018). Therefore, at low temperatures, there is a higher chance that an RO q 2 radical will be lost before it reaches a high oxygenation level and forms a HOM that can be detected by the nitrate CI-APi-TOF.…”

Section: Effect Of Temperature On α-Pinene Oxidation and Hom Formationmentioning

confidence: 99%

Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C

et al. 2020

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Abstract. Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 ∘C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 ∘C to 0.7 % at −50 ∘C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at −50 ∘C compared with 25 ∘C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

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“…On the other hand, lower temperatures lead to decreased autooxidation reaction rates and reduced yields of HOM. Recent studies have shown that the former effect compensates for the latter effect, having an overall increase in nucleation and growth rates at lower temperatures (Stolzenburg et al, 2018;Simon et al, 2020;Ye et al, 2019). While these mechanisms are clear in chamber studies, the situation becomes more complicated in the atmosphere because of the complexity of the atmosphere-biosphere system having simultaneous temperature-dependent processes that can enhance or suppress NPF, making current atmospheric observations inconsistent on the role of temperature on NPF (Kerminen et al, 2018).…”

Section: The Driving Atmospheric Parameters Of the Npf Eventsmentioning

confidence: 99%

Towards understanding the mechanisms of new particle formation in the Eastern Mediterranean

Baalbaki

Pikridas

Jokinen

et al. 2020

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Abstract. To quantify the contribution of new particle formation (NPF) to ultrafine particle number and CCN budgets, one has to understand the mechanisms that govern NPF in different environments and its temporal extent. Here, we study NPF in Cyprus, an Eastern Mediterranean country located at the crossroads of three continents. We performed one-year continuous measurements of aerosol particles down to ~ 1 nm in diameter, for the first time in the Eastern Mediterranean and Middle East (EMME) region. These measurements were complemented with trace gas data, meteorological variables and retroplume analysis. We show that NPF is a very frequent phenomenon at this site and has higher frequencies of occurrence during spring and autumn. NPF events were both of local and regional origin, and the local events occurred frequently during the month with the lowest NPF frequency. Some NPF events exhibited multiple onsets, while others exhibited particle apparent shrinkage in size. Additionally, NPF events were observed during the night-time and during episodes of high desert dust loadings. Particle formation rates and growth rates were comparable to those in urban environments, although our site is a rural one. Meteorological variables and trace gases played a role in explaining the intra-monthly variability of NPF events, but did not explain why summer month had the least NPF frequency. Similarly, pre-existing aerosol loading did not explain the observed seasonality. The month with the least NPF frequency were associated with higher H2SO4 concentrations but lower NOx concentration, which is an indicator of anthropogenic influence. Air masses arriving from the Middle East were not observed during these month, which could suggest that precursor vapors important for nucleation and growth are transported to our site from the Middle East. Further comprehensive measurements of precursor vapors are required to prove this hypothesis.

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Molecular Composition and Volatility of Nucleated Particles from α-Pinene Oxidation between −50 °C and +25 °C

Cited by 46 publications

References 45 publications

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C

Towards understanding the mechanisms of new particle formation in the Eastern Mediterranean

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Molecular Composition and Volatility of Nucleated Particles from α-Pinene Oxidation between −50 °C and +25 °C

Cited by 46 publications

References 45 publications

Chemical composition of nanoparticles from &lt;i&gt;α&lt;/i&gt;-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Chemical composition of nanoparticles from &lt;i&gt;α&lt;/i&gt;-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C

Towards understanding the mechanisms of new particle formation in the Eastern Mediterranean

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Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature