Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation
Carla Frege
(1)
,
Ismael Ortega
(2)
,
Matti Rissanen
(3)
,
Arnaud Praplan
(3)
,
Gerhard Steiner
(3, 4, 5)
,
Martin Heinritzi
(6)
,
Lauri Ahonen
(3)
,
António Amorim
(7)
,
Anne-Kathrin Bernhammer
(4, 8)
,
Federico Bianchi
(1)
,
Sophia Brilke
(4, 5, 6)
,
Martin Breitenlechner
(4, 9)
,
Lubna Dada
(3)
,
António Dias
(7)
,
Jonathan Duplissy
(3, 10)
,
Sébastian Ehrhart
(10, 11)
,
Imad El-Haddad
(1)
,
Lukas Fischer
(4)
,
Claudia Fuchs
(1)
,
Olga Garmash
(3)
,
Marc Gonin
(12)
,
Armin Hansel
(4, 8)
,
Christopher Hoyle
(1)
,
Tuija Jokinen
(3)
,
Heikki Junninen
(3, 13)
,
Jasper Kirkby
(6, 10)
,
Andrea Kürten
(6)
,
Katrianne Lehtipalo
(1, 3)
,
Markus Leiminger
(4, 6)
,
Roy Lee Mauldin
(3, 14)
,
Ugo Molteni
(1)
,
Leonid Nichman
(15)
,
Tuukka Petäjä
(3)
,
Nina Sarnela
(3)
,
Siegfried Schobesberger
(3, 16)
,
Mario Simon
(6)
,
Mikko Sipilä
(3)
,
Dominik Stolzenburg
(5)
,
Antonio Tomé
(17)
,
Alexander Vogel
(1, 10)
,
Andrea C. Wagner
(6)
,
Robert Wagner
(3)
,
Mao Xiao
(1)
,
Chao Yan
(3)
,
Penglin Ye
(18, 19)
,
Joachim Curtius
(4)
,
Neil Donahue
(18)
,
Richard Flagan
(20)
,
Markku Kulmala
(3)
,
Douglas R. Worsnop
(3, 16, 19)
,
Paul Winkler
(5)
,
Josef Dommen
(1)
,
Urs Baltensperger
(1)
1
PSI -
Paul Scherrer Institute
2 ONERA - The French Aerospace Lab [Palaiseau]
3 Helsingin yliopisto = Helsingfors universitet = University of Helsinki
4 Leopold Franzens Universität Innsbruck - University of Innsbruck
5 Universität Wien = University of Vienna
6 IAU - Institute for Atmospheric and Environmental Sciences [Frankfurt/Main]
7 ULISBOA - Universidade de Lisboa = University of Lisbon = Université de Lisbonne
8 Ionicon Analytik GmbH
9 Harvard University
10 CERN [Genève]
11 Atmospheric Chemistry Department [MPIC]
12 Tofwerk AG
13 University of Tartu
14 ATOC - Department of Atmospheric and Oceanic Sciences [Boulder]
15 SEES - School of Earth and Environmental Sciences [Manchester]
16 University of Eastern Finland
17 UBI - University of Beira Interior [Portugal]
18 CAPS - Center for Atmospheric Particle Studies [Pittsburgh]
19 Aerodyne Research Inc.
20 CALTECH - California Institute of Technology
2 ONERA - The French Aerospace Lab [Palaiseau]
3 Helsingin yliopisto = Helsingfors universitet = University of Helsinki
4 Leopold Franzens Universität Innsbruck - University of Innsbruck
5 Universität Wien = University of Vienna
6 IAU - Institute for Atmospheric and Environmental Sciences [Frankfurt/Main]
7 ULISBOA - Universidade de Lisboa = University of Lisbon = Université de Lisbonne
8 Ionicon Analytik GmbH
9 Harvard University
10 CERN [Genève]
11 Atmospheric Chemistry Department [MPIC]
12 Tofwerk AG
13 University of Tartu
14 ATOC - Department of Atmospheric and Oceanic Sciences [Boulder]
15 SEES - School of Earth and Environmental Sciences [Manchester]
16 University of Eastern Finland
17 UBI - University of Beira Interior [Portugal]
18 CAPS - Center for Atmospheric Particle Studies [Pittsburgh]
19 Aerodyne Research Inc.
20 CALTECH - California Institute of Technology
Jonathan Duplissy
- Fonction : Auteur
- PersonId : 1189336
- ORCID : 0000-0001-8819-0264
- IdRef : 26705131X
Tuija Jokinen
- Fonction : Auteur
- PersonId : 779621
- ORCID : 0000-0002-1280-1396
Tuukka Petäjä
- Fonction : Auteur
- PersonId : 779400
- ORCID : 0000-0002-1881-9044
Mikko Sipilä
- Fonction : Auteur
- PersonId : 852222
Joachim Curtius
- Fonction : Auteur
- PersonId : 775517
- ORCID : 0000-0003-3153-4630
Markku Kulmala
- Fonction : Auteur
- PersonId : 763836
- ORCID : 0000-0003-3464-7825
- IdRef : 15928953X
Résumé
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 (NO3−) 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 (NH4+) 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 C30 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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