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Published August 3, 2020 | Supplemental Material + Published
Journal Article Open

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

Simon, Mario ORCID icon
Dada, Lubna ORCID icon
Heinritzi, Martin
Scholz, Wiebke ORCID icon
Stolzenburg, Dominik ORCID icon
Fischer, Lukas ORCID icon
Wagner, Andrea C. ORCID icon
Kürten, Andreas
Rörup, Birte
He, Xu-Cheng ORCID icon
Almeida, João
Baalbaki, Rima ORCID icon
Baccarini, Andrea ORCID icon
Bauer, Paulus S. ORCID icon
Beck, Lisa ORCID icon
Bergen, Anton
Bianchi, Federico ORCID icon
Bräkling, Steffen
Brilke, Sophia ORCID icon
Caudillo, Lucia
Chen, Dexian ORCID icon
Chu, Biwu ORCID icon
Dias, António
Draper, Danielle C.
Duplissy, Jonathan
El-Haddad, Imad
Finkenzeller, Henning ORCID icon
Frege, Carla ORCID icon
Gonzalez-Carracedo, Loic
Gordon, Hamish ORCID icon
Granzin, Manuel
Hakala, Jani
Hofbauer, Victoria
Hoyle, Christopher R. ORCID icon
Kim, Changhyuk ORCID icon
Kong, Weimeng ORCID icon
Lamkaddam, Houssni
Lee, Chuan P. ORCID icon
Lehtipalo, Katrianne ORCID icon
Leiminger, Markus ORCID icon
Mai, Huajun ORCID icon
Manninen, Hanna E.
Marie, Guillaume ORCID icon
Marten, Ruby ORCID icon
Mentler, Bernhard
Molteni, Ugo ORCID icon
Nichman, Leonid ORCID icon
Nie, Wei
Ojdanic, Andrea
Onnela, Antti
Partoll, Eva
Petäjä, Tuukka ORCID icon
Pfeifer, Joschka ORCID icon
Philippov, Maxim ORCID icon
Quéléver, Lauriane L. J.
Ranjithkumar, Ananth
Rissanen, Matti P. ORCID icon
Schallhart, Simon
Schobesberger, Siegfried ORCID icon
Schuchmann, Simone
Shen, Jiali
Sipilä, Mikko
Steiner, Gerhard
Stozhkov, Yuri
Tauber, Christian ORCID icon
Tham, Yee J. ORCID icon
Tomé, António R.
Vazquez-Pufleau, Miguel
Vogel, Alexander L. ORCID icon
Wagner, Robert
Wang, Mingyi
Wang, Dongyu S. ORCID icon
Wang, Yonghong ORCID icon
Weber, Stefan K. ORCID icon
Wu, Yusheng
Xiao, Mao
Yan, Chao ORCID icon
Ye, Penglin ORCID icon
Ye, Qing
Zauner-Wieczorek, Marcel ORCID icon
Zhou, Xueqin
Baltensperger, Urs
Dommen, Josef ORCID icon
Flagan, Richard C. ORCID icon
Hansel, Armin ORCID icon
Kulmala, Markku ORCID icon
Volkamer, Rainer ORCID icon
Winkler, Paul M.
Worsnop, Douglas R.
Donahue, Neil M. ORCID icon
Kirkby, Jasper ORCID icon
Curtius, Joachim ORCID icon

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 (J_(1.7 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.

Additional Information

© Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 15 Nov 2019 – Discussion started: 21 Jan 2020 – Revised: 27 May 2020 – Accepted: 19 Jun 2020 – Published: 03 Aug 2020. We thank Patrick Carrie, Louis-Philippe De Menezes, Jonathan Dumollard, Katja Ivanova, Francisco Josa, Timo Keber, Ilia Krasin, Robert Kristic, Abdelmajid Laassiri, Osman Maksumov, Frank Malkemper, Benjamin Marichy, Herve Martinati, Sergey Vitaljevich Mizin, Robert Sitals, Albin Wasem, and Mats Wilhelmsson for their contributions to the experiment. This research has received funding from the German Federal Ministry of Education and Research, CLOUD-12 (01LK1222A) and CLOUD-16 (01LK1601A); the European Commission Seventh Framework Programme and European Union Horizon 2020 program (Marie Skłodowska Curie ITNs no. 316662 "CLOUD-TRAIN", no. 764991 "CLOUD-MOTION", MSCA-IF no. 656994 "nano-CAVa", and MC-COFUND grant no. 600377); the European Research Council (ERC; project nos. 692891 "DAMOCLES", 638703 "COALA", 616075 "NANODYNAMITE", 335478 "QAPPA", 742206 "ATM-GP", 714621 "GASPARCON"); the Swiss National Science Foundation (project nos. 20020_152907, 200020_172602, 20FI20_159851, 20FI20_172622); the Academy of Finland (Centre of Excellence no. 307331, projects 299574, 296628, 306853, 304013, 310682); the Finnish Funding Agency for Technology and Innovation; the Väisälä Foundation; the Nessling Foundation; the Austrian Science Fund (FWF; project no. J3951-N36, project no. P27295-N20); the Austrian Research Promotion Agency (FFG, project no. 846050); the Portuguese Foundation for Science and Technology (project no. CERN/FIS-COM/0014/2017); the Swedish Research Council Formas (project number 2015-749); Vetenskapsrådet (grant 2011-5120); the Presidium of the Russian Academy of Sciences and Russian Foundation for Basic Research (grants 08-02-91006-CERN, 12-02-91522-CERN); the US National Science Foundation (grant nos. AGS1136479, AGS1447056, AGS1439551, CHE1012293, AGS1649147, AGS1602086, AGS1801280, AGS1801329, AGS1801574 and AGS1801897); the Wallace Research Foundation; the US Department of Energy (grant DE-SC0014469); the NERC GASSP project NE/J024252/1m; the Royal Society (Wolfson Merit Award); the UK Natural Environment Research Council (grant no. NE/K015966/1); Dreyfus Award EP-11-117; the French National Research Agency through the PIA (Programme d'Investissement d'Avenir), the Regional Council Nord-Pas de Calais, and the European Funds for Regional Economic Development Labex-Cappa (grant no. ANR-11-LABX-0005-01). Data availability: Data related to this article are available upon request to the corresponding authors. The supplement related to this article is available online at: https://doi.org/10.5194/acp-20-9183-2020-supplement. Author contributions: MSim, LD, MH, WS, DS, LF, ACW, BR, AK, XH, JA, RB, ABa, ABe, FB, SBrä, LC, DC, BC, AD, JDu, IE, HF, CF, LG, HG, MG, JH, VH, CK, WK, HL, CPL, KL, ML, HM, HEM, GM, BM, UM, AOn, EP, TP, JP, MP, LLJQ, MPR, SScho, SSchu, JS, MSip, GS, YS, YJT, ART, MV, AV, RW, MW, DSW, YW, SKW, YW, CY, PY, QY, MZ, XZ, RCF, RV, PMW and JK contributed to the development of the CLOUD facility and analysis instruments. MSim, LD, MH, WS, DS, LF, ACW, BR, XH, JA, RB, ABa, PSB, LB, ABe, FB, SBrä, SBri, LC, AD, DCD, JDu, IE, HF, LG, HG, MG, JH, VH, CRH, CK, WK, HL, CPL, KL, ML, HEM, GM, RM, BM, UM, LN, WN, AOj, EP, JP, LLJQ, AR, MPR, SScha, SSchu, JS, GS, YS, CT, YJT, ART, MV, AV, RW, DSW, YW, SKW, YW, MX, CY, PY, MZ, PMW and JK collected the data. MSim, LD, MH, WS, LF, ACW, BR, LG, CK, GM, BM, SKW, PY and RV performed modeling and analyzed the data. MSim, LD, MH, WS, DS, LF, ACW, BR, AK, HG, BM, UM, TP, MPR, PY, UB, JDo, RCF, AH, MK, DRW, NMD, JK and JC were involved in the scientific discussion and interpretation of the results. MSim, LD, MH, WS, AK, AV, UB, JDo, RCF, NMD, JK and JC contributed to the writing and editing of the manuscript. The authors declare that they have no conflict of interest. Special issue statement: This article is part of the special issue "The CERN CLOUD experiment (ACP/AMT inter-journal SI)". It is not associated with a conference. Review statement: This paper was edited by Manish Shrivastava and reviewed by two anonymous referees.

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Created:
August 19, 2023
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October 20, 2023