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

Simon, Mario and Dada, Lubna and Heinritzi, Martin and Scholz, Wiebke and Stolzenburg, Dominik and Fischer, Lukas and Wagner, Andrea C. and Kürten, Andreas and Rörup, Birte and He, Xu-Cheng and Almeida, João and Baalbaki, Rima and Baccarini, Andrea and Bauer, Paulus S. and Beck, Lisa and Bergen, Anton and Bianchi, Federico and Bräkling, Steffen and Brilke, Sophia and Caudillo, Lucia and Chen, Dexian and Chu, Biwu and Dias, António and Draper, Danielle C. and Duplissy, Jonathan and El-Haddad, Imad and Finkenzeller, Henning and Frege, Carla and Gonzalez-Carracedo, Loic and Gordon, Hamish and Granzin, Manuel and Hakala, Jani and Hofbauer, Victoria and Hoyle, Christopher R. and Kim, Changhyuk and Kong, Weimeng and Lamkaddam, Houssni and Lee, Chuan P. and Lehtipalo, Katrianne and Leiminger, Markus and Mai, Huajun and Manninen, Hanna E. and Marie, Guillaume and Marten, Ruby and Mentler, Bernhard and Molteni, Ugo and Nichman, Leonid and Nie, Wei and Ojdanic, Andrea and Onnela, Antti and Partoll, Eva and Petäjä, Tuukka and Pfeifer, Joschka and Philippov, Maxim and Quéléver, Lauriane L. J. and Ranjithkumar, Ananth and Rissanen, Matti P. and Schallhart, Simon and Schobesberger, Siegfried and Schuchmann, Simone and Shen, Jiali and Sipilä, Mikko and Steiner, Gerhard and Stozhkov, Yuri and Tauber, Christian and Tham, Yee J. and Tomé, António R. and Vazquez-Pufleau, Miguel and Vogel, Alexander L. and Wagner, Robert and Wang, Mingyi and Wang, Dongyu S. and Wang, Yonghong and Weber, Stefan K. and Wu, Yusheng and Xiao, Mao and Yan, Chao and Ye, Penglin and Ye, Qing and Zauner-Wieczorek, Marcel and Zhou, Xueqin and Baltensperger, Urs and Dommen, Josef and Flagan, Richard C. and Hansel, Armin and Kulmala, Markku and Volkamer, Rainer and Winkler, Paul M. and Worsnop, Douglas R. and Donahue, Neil M. and Kirkby, Jasper and Curtius, Joachim (2020) Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C. Atmospheric Chemistry and Physics, 20 (15). pp. 9183-9207. ISSN 1680-7324.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription
Simon, Mario0000-0002-4900-7460
Dada, Lubna0000-0003-1105-9043
Scholz, Wiebke0000-0003-2617-620X
Stolzenburg, Dominik0000-0003-1014-1360
Fischer, Lukas0000-0002-3141-9088
Wagner, Andrea C.0000-0003-3159-9434
He, Xu-Cheng0000-0002-7416-306X
Baalbaki, Rima0000-0002-4480-2107
Baccarini, Andrea0000-0003-4614-247X
Bauer, Paulus S.0000-0002-0014-3082
Beck, Lisa0000-0003-3700-5895
Bianchi, Federico0000-0003-2996-3604
Brilke, Sophia0000-0003-3133-249X
Chen, Dexian0000-0001-6963-5205
Chu, Biwu0000-0002-7548-5669
Finkenzeller, Henning0000-0002-8349-3714
Frege, Carla0000-0001-7833-8771
Gordon, Hamish0000-0002-1822-3224
Hoyle, Christopher R.0000-0002-1369-9143
Kim, Changhyuk0000-0002-8744-4880
Kong, Weimeng0000-0002-9432-2857
Lee, Chuan P.0000-0003-0051-8179
Lehtipalo, Katrianne0000-0002-1660-2706
Leiminger, Markus0000-0003-3343-5425
Mai, Huajun0000-0002-0616-1986
Marie, Guillaume0000-0003-1454-0908
Marten, Ruby0000-0003-0417-4350
Molteni, Ugo0000-0002-1623-1933
Nichman, Leonid0000-0003-3923-1589
Petäjä, Tuukka0000-0002-1881-9044
Pfeifer, Joschka0000-0002-9172-4447
Philippov, Maxim0000-0003-4302-0020
Rissanen, Matti P.0000-0003-0463-8098
Schobesberger, Siegfried0000-0002-5777-4897
Tauber, Christian0000-0003-1453-1067
Tham, Yee J.0000-0001-7924-5841
Vogel, Alexander L.0000-0002-1293-6370
Wang, Dongyu S.0000-0001-7549-1578
Wang, Yonghong0000-0003-2498-9143
Weber, Stefan K.0000-0001-7408-9069
Yan, Chao0000-0002-5735-9597
Ye, Penglin0000-0002-6954-4028
Zauner-Wieczorek, Marcel0000-0002-0867-665X
Dommen, Josef0000-0002-0006-0009
Flagan, Richard C.0000-0001-5690-770X
Hansel, Armin0000-0002-1062-2394
Kulmala, Markku0000-0003-3464-7825
Volkamer, Rainer0000-0002-0899-1369
Donahue, Neil M.0000-0003-3054-2364
Kirkby, Jasper0000-0003-2341-9069
Curtius, Joachim0000-0003-3153-4630
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: 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.
Funding AgencyGrant Number
Bundesministerium für Bildung und Forschung (BMBF)01LK1222A
Bundesministerium für Bildung und Forschung (BMBF)01LK1601A
Marie Curie Fellowship316662
Marie Curie Fellowship764991
Marie Curie Fellowship656994
Marie Curie Fellowship600377
European Research Council (ERC)692891
European Research Council (ERC)638703
European Research Council (ERC)616075
European Research Council (ERC)335478
European Research Council (ERC)742206
European Research Council (ERC)714621
Swiss National Science Foundation (SNSF)20020_152907
Swiss National Science Foundation (SNSF)200020_172602
Swiss National Science Foundation (SNSF)20FI20_159851
Swiss National Science Foundation (SNSF)20FI20_172622
Academy of Finland307331
Academy of Finland299574
Academy of Finland296628
Academy of Finland306853
Academy of Finland304013
Academy of Finland310682
Finnish Funding Agency for Technology and InnovationUNSPECIFIED
Väisälä FoundationUNSPECIFIED
Nessling FoundationUNSPECIFIED
FWF Der WissenschaftsfondsJ3951-N36
FWF Der WissenschaftsfondsP27295-N20
Österreichische Forschungsförderungsgesellschaft846050
Fundação para a Ciência e a Tecnologia (FCT)CERN/FIS-COM/0014/2017
Swedish Research Council2015-749
Presidium of the Russian Academy of SciencesUNSPECIFIED
Russian Foundation for Basic Research08-02-91006-CERN
Russian Foundation for Basic Research12-02-91522-CERN
Wallace Research FoundationUNSPECIFIED
Department of Energy (DOE)DE-SC0014469
Natural Environment Research Council (NERC)NE/J024252/1m
Natural Environment Research Council (NERC)NE/K015966/1
Camille and Henry Dreyfus FoundationEP-11-117
Agence Nationale pour la Recherche (ANR)ANR-11-LABX-0005-01
Regional Council Nord-Pas de CalaisUNSPECIFIED
European Funds for Regional Economic DevelopmentUNSPECIFIED
Issue or Number:15
Record Number:CaltechAUTHORS:20200831-092827810
Persistent URL:
Official Citation:Simon, M., Dada, L., Heinritzi, M., Scholz, W., Stolzenburg, D., Fischer, L., Wagner, A. C., Kürten, A., Rörup, B., He, X.-C., Almeida, J., Baalbaki, R., Baccarini, A., Bauer, P. S., Beck, L., Bergen, A., Bianchi, F., Bräkling, S., Brilke, S., Caudillo, L., Chen, D., Chu, B., Dias, A., Draper, D. C., Duplissy, J., El-Haddad, I., Finkenzeller, H., Frege, C., Gonzalez-Carracedo, L., Gordon, H., Granzin, M., Hakala, J., Hofbauer, V., Hoyle, C. R., Kim, C., Kong, W., Lamkaddam, H., Lee, C. P., Lehtipalo, K., Leiminger, M., Mai, H., Manninen, H. E., Marie, G., Marten, R., Mentler, B., Molteni, U., Nichman, L., Nie, W., Ojdanic, A., Onnela, A., Partoll, E., Petäjä, T., Pfeifer, J., Philippov, M., Quéléver, L. L. J., Ranjithkumar, A., Rissanen, M. P., Schallhart, S., Schobesberger, S., Schuchmann, S., Shen, J., Sipilä, M., Steiner, G., Stozhkov, Y., Tauber, C., Tham, Y. J., Tomé, A. R., Vazquez-Pufleau, M., Vogel, A. L., Wagner, R., Wang, M., Wang, D. S., Wang, Y., Weber, S. K., Wu, Y., Xiao, M., Yan, C., Ye, P., Ye, Q., Zauner-Wieczorek, M., Zhou, X., Baltensperger, U., Dommen, J., Flagan, R. C., Hansel, A., Kulmala, M., Volkamer, R., Winkler, P. M., Worsnop, D. R., Donahue, N. M., Kirkby, J., and Curtius, J.: Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C, Atmos. Chem. Phys., 20, 9183–9207,, 2020
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ID Code:105160
Deposited By: Tony Diaz
Deposited On:08 Sep 2020 18:59
Last Modified:08 Sep 2020 18:59

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