Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

Joao Almeida; Siegfried Schobesberger; Andreas Kuerten; Ismael K. Ortega; Oona Kupiainen-Maatta; Arnaud P. Praplan; Alexey Adamov; Antonio Amorim; Federico Bianchi; Martin Breitenlechner; Andre David; Josef Dommen; Neil M. Donahue; Andrew Downard; Eimear Dunne; Jonathan Duplissy; Sebastian Ehrhart; Richard C. Flagan; Alessandro Franchin; Roberto Guida; Jani Hakala; Armin Hansel; Martin Heinritzi; Henning Henschel; Tuija Jokinen; Heikki Junninen; Maija Kajos; Juha Kangasluoma; Helmi Keskinen; Agnieszka Kupc; Theo Kurten; Alexander N. Kvashin; Ari Laaksonen; Katrianne Lehtipalo; Markus Leiminger; Johannes Leppa; Ville Loukonen; Vladimir Makhmutov; Serge Mathot; Matthew J. McGrath; Tuomo Nieminen; Tinja Olenius; Antti Onnela; Tuukka Petaja; Francesco Riccobono; Ilona Riipinen; Matti Rissanen; Linda Rondo; Taina Ruuskanen; Filipe D. Santos; Nina Sarnela; Simon Schallhart; Ralf Schnitzhofer; John H. Seinfeld; Mario Simon; Mikko Sipila; Yuri Stozhkov; Frank Stratmann; Antonio Tome; Jasmin Troestl; Georgios Tsagkogeorgas; Petri Vaattovaara; Yrjo Viisanen; Annele Virtanen; Aron Vrtala; Paul E. Wagner; Ernest Weingartner; Heike Wex; Christina Williamson; Daniela Wimmer; Penglin Ye; Taina Yli-Juuti; Kenneth S. Carslaw; Markku Kulmala; Joachim Curtius; Urs Baltensperger; Douglas R. Worsnop; Hanna Vehkamaki; Jasper Kirkby

doi:10.1038/nature12663

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

Joao Almeida
, Siegfried Schobesberger
, Andreas Kuerten
, Ismael K. Ortega
, Oona Kupiainen-Maatta
, Arnaud P. Praplan
, Alexey Adamov
, Antonio Amorim
, Federico Bianchi
, Martin Breitenlechner
, Andre David
, Josef Dommen
, Neil M. Donahue
, Andrew Downard
, Eimear Dunne
, Jonathan Duplissy
, Sebastian Ehrhart
, Richard C. Flagan
, Alessandro Franchin
, Roberto Guida

Jani Hakala, Armin Hansel, Martin Heinritzi, Henning Henschel, Tuija Jokinen, Heikki Junninen, Maija Kajos, Juha Kangasluoma, Helmi Keskinen, Agnieszka Kupc, Theo Kurten, Alexander N. Kvashin, Ari Laaksonen, Katrianne Lehtipalo, Markus Leiminger, Johannes Leppa, Ville Loukonen, Vladimir Makhmutov, Serge Mathot, Matthew J. McGrath, Tuomo Nieminen, Tinja Olenius, Antti Onnela, Tuukka Petaja, Francesco Riccobono, Ilona Riipinen, Matti Rissanen, Linda Rondo, Taina Ruuskanen, Filipe D. Santos, Nina Sarnela, Simon Schallhart, Ralf Schnitzhofer, John H. Seinfeld, Mario Simon, Mikko Sipila, Yuri Stozhkov, Frank Stratmann, Antonio Tome, Jasmin Troestl, Georgios Tsagkogeorgas, Petri Vaattovaara, Yrjo Viisanen, Annele Virtanen, Aron Vrtala, Paul E. Wagner, Ernest Weingartner, Heike Wex, Christina Williamson, Daniela Wimmer, Penglin Ye, Taina Yli-Juuti, Kenneth S. Carslaw, Markku Kulmala, Joachim Curtius, Urs Baltensperger, Douglas R. Worsnop, Hanna Vehkamaki, Jasper Kirkby (Corresponding author)

Aerosol Physics and Environmental Physics

Publications: Contribution to journal › Article › Peer Reviewed

Abstract

Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei¹. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes². Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases². However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere³. It is thought that amines may enhance nucleation^{4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16}, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.

Original language	English
Pages (from-to)	359-363
Number of pages	11
Journal	Nature
Volume	502
Issue number	7471
DOIs	https://doi.org/10.1038/nature12663
Publication status	Published - 17 Oct 2013

Funding

We thank J.-L. Agostini, P. Carrie, L.-P. De Menezes, F. Josa, I. Krasin, R. Kristic, O. S. Maksumov, S. V. Mizin, R. Sitals, A. Wasem and M. Wilhelmsson for their contributions to the experiment, and D. Hanson and P. McMurry for discussions on their unpublished measurements of ambient gas-phase amines. We thank the CSC Centre for Scientific Computing in Espoo, Finland, for computer time, and J. Pierce and P. Paasonen for discussions. We thank CERN for supporting CLOUD with technicalandfinancial resources, and for providinga particlebeamfromtheCERN Proton Synchrotron. This research received funding from the EC Seventh Framework Programme (Marie Curie Initial Training Network 'CLOUD-ITN' no. 215072, MC-ITN 'CLOUD-TRAIN' no. 316662, ERC-Starting 'MOCAPAF' grant 57360 and ERC-Advanced 'ATMNUCLE' grant 227463), the German Federal Ministry of Education and Research (projects 01LK0902A and 01LK1222A), the Swiss National Science Foundation (projects 200020_135307 and 206620_130527), the Academy of Finland (Center of Excellence project 1118615), the Academy of Finland (135054, 133872, 251427, 139656, 139995, 137749, 141217 and 141451), the Finnish Funding Agency for Technology and Innovation, the Vaisala Foundation, the Nessling Foundation, the Austrian Science Fund (FWF; projects P19546 and L593), the Portuguese Foundation for Science and Technology (project CERN/FP/116387/2010), the Swedish Research Council, Vetenskapsradet (grant 2011-5120), the Presidium of the Russian Academy of Sciences and Russian Foundation for Basic Research (grants 08-02-91006-CERN and 12-02-91522-CERN), and the US National Science Foundation (grants AGS1136479 and CHE1012293).

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 13 Climate Action

Austrian Fields of Science 2012

105204 Climatology
105206 Meteorology
105904 Environmental research

Keywords

IONIZATION MASS-SPECTROMETRY
FORMATION EVENTS
AEROSOL NUCLEATION
ALIPHATIC-AMINES
BOREAL FOREST
AMMONIA
NANOPARTICLES
DIMETHYLAMINE
RATES
WATER

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10.1038/nature12663

Cite this

Almeida, J., Schobesberger, S., Kuerten, A., Ortega, I. K., Kupiainen-Maatta, O., Praplan, A. P., Adamov, A., Amorim, A., Bianchi, F., Breitenlechner, M., David, A., Dommen, J., Donahue, N. M., Downard, A., Dunne, E., Duplissy, J., Ehrhart, S., Flagan, R. C., Franchin, A., ... Kirkby, J. (2013). Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere. Nature, 502(7471), 359-363. https://doi.org/10.1038/nature12663

@article{8ff5f4e1582b469482f1896d0b511b36,

title = "Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere",

abstract = "Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei1. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes2. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases2. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere3. It is thought that amines may enhance nucleation4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.",

keywords = "IONIZATION MASS-SPECTROMETRY, FORMATION EVENTS, AEROSOL NUCLEATION, ALIPHATIC-AMINES, BOREAL FOREST, AMMONIA, NANOPARTICLES, DIMETHYLAMINE, RATES, WATER",

author = "Joao Almeida and Siegfried Schobesberger and Andreas Kuerten and Ortega, \{Ismael K.\} and Oona Kupiainen-Maatta and Praplan, \{Arnaud P.\} and Alexey Adamov and Antonio Amorim and Federico Bianchi and Martin Breitenlechner and Andre David and Josef Dommen and Donahue, \{Neil M.\} and Andrew Downard and Eimear Dunne and Jonathan Duplissy and Sebastian Ehrhart and Flagan, \{Richard C.\} and Alessandro Franchin and Roberto Guida and Jani Hakala and Armin Hansel and Martin Heinritzi and Henning Henschel and Tuija Jokinen and Heikki Junninen and Maija Kajos and Juha Kangasluoma and Helmi Keskinen and Agnieszka Kupc and Theo Kurten and Kvashin, \{Alexander N.\} and Ari Laaksonen and Katrianne Lehtipalo and Markus Leiminger and Johannes Leppa and Ville Loukonen and Vladimir Makhmutov and Serge Mathot and McGrath, \{Matthew J.\} and Tuomo Nieminen and Tinja Olenius and Antti Onnela and Tuukka Petaja and Francesco Riccobono and Ilona Riipinen and Matti Rissanen and Linda Rondo and Taina Ruuskanen and Santos, \{Filipe D.\} and Nina Sarnela and Simon Schallhart and Ralf Schnitzhofer and Seinfeld, \{John H.\} and Mario Simon and Mikko Sipila and Yuri Stozhkov and Frank Stratmann and Antonio Tome and Jasmin Troestl and Georgios Tsagkogeorgas and Petri Vaattovaara and Yrjo Viisanen and Annele Virtanen and Aron Vrtala and Wagner, \{Paul E.\} and Ernest Weingartner and Heike Wex and Christina Williamson and Daniela Wimmer and Penglin Ye and Taina Yli-Juuti and Carslaw, \{Kenneth S.\} and Markku Kulmala and Joachim Curtius and Urs Baltensperger and Worsnop, \{Douglas R.\} and Hanna Vehkamaki and Jasper Kirkby",

year = "2013",

month = oct,

day = "17",

doi = "10.1038/nature12663",

language = "English",

volume = "502",

pages = "359--363",

journal = "Nature",

issn = "0028-0836",

publisher = "NATURE PUBLISHING GROUP",

number = "7471",

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Almeida, J, Schobesberger, S, Kuerten, A, Ortega, IK, Kupiainen-Maatta, O, Praplan, AP, Adamov, A, Amorim, A, Bianchi, F, Breitenlechner, M, David, A, Dommen, J, Donahue, NM, Downard, A, Dunne, E, Duplissy, J, Ehrhart, S, Flagan, RC, Franchin, A, Guida, R, Hakala, J, Hansel, A, Heinritzi, M, Henschel, H, Jokinen, T, Junninen, H, Kajos, M, Kangasluoma, J, Keskinen, H, Kupc, A, Kurten, T, Kvashin, AN, Laaksonen, A, Lehtipalo, K, Leiminger, M, Leppa, J, Loukonen, V, Makhmutov, V, Mathot, S, McGrath, MJ, Nieminen, T, Olenius, T, Onnela, A, Petaja, T, Riccobono, F, Riipinen, I, Rissanen, M, Rondo, L, Ruuskanen, T, Santos, FD, Sarnela, N, Schallhart, S, Schnitzhofer, R, Seinfeld, JH, Simon, M, Sipila, M, Stozhkov, Y, Stratmann, F, Tome, A, Troestl, J, Tsagkogeorgas, G, Vaattovaara, P, Viisanen, Y, Virtanen, A, Vrtala, A, Wagner, PE, Weingartner, E, Wex, H, Williamson, C, Wimmer, D, Ye, P, Yli-Juuti, T, Carslaw, KS, Kulmala, M, Curtius, J, Baltensperger, U, Worsnop, DR, Vehkamaki, H & Kirkby, J 2013, 'Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere', Nature, vol. 502, no. 7471, pp. 359-363. https://doi.org/10.1038/nature12663

TY - JOUR

T1 - Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

AU - Almeida, Joao

AU - Schobesberger, Siegfried

AU - Kuerten, Andreas

AU - Ortega, Ismael K.

AU - Kupiainen-Maatta, Oona

AU - Praplan, Arnaud P.

AU - Adamov, Alexey

AU - Amorim, Antonio

AU - Bianchi, Federico

AU - Breitenlechner, Martin

AU - David, Andre

AU - Dommen, Josef

AU - Donahue, Neil M.

AU - Downard, Andrew

AU - Dunne, Eimear

AU - Duplissy, Jonathan

AU - Ehrhart, Sebastian

AU - Flagan, Richard C.

AU - Franchin, Alessandro

AU - Guida, Roberto

AU - Hakala, Jani

AU - Hansel, Armin

AU - Heinritzi, Martin

AU - Henschel, Henning

AU - Jokinen, Tuija

AU - Junninen, Heikki

AU - Kajos, Maija

AU - Kangasluoma, Juha

AU - Keskinen, Helmi

AU - Kupc, Agnieszka

AU - Kurten, Theo

AU - Kvashin, Alexander N.

AU - Laaksonen, Ari

AU - Lehtipalo, Katrianne

AU - Leiminger, Markus

AU - Leppa, Johannes

AU - Loukonen, Ville

AU - Makhmutov, Vladimir

AU - Mathot, Serge

AU - McGrath, Matthew J.

AU - Nieminen, Tuomo

AU - Olenius, Tinja

AU - Onnela, Antti

AU - Petaja, Tuukka

AU - Riccobono, Francesco

AU - Riipinen, Ilona

AU - Rissanen, Matti

AU - Rondo, Linda

AU - Ruuskanen, Taina

AU - Santos, Filipe D.

AU - Sarnela, Nina

AU - Schallhart, Simon

AU - Schnitzhofer, Ralf

AU - Seinfeld, John H.

AU - Simon, Mario

AU - Sipila, Mikko

AU - Stozhkov, Yuri

AU - Stratmann, Frank

AU - Tome, Antonio

AU - Troestl, Jasmin

AU - Tsagkogeorgas, Georgios

AU - Vaattovaara, Petri

AU - Viisanen, Yrjo

AU - Virtanen, Annele

AU - Vrtala, Aron

AU - Wagner, Paul E.

AU - Weingartner, Ernest

AU - Wex, Heike

AU - Williamson, Christina

AU - Wimmer, Daniela

AU - Ye, Penglin

AU - Yli-Juuti, Taina

AU - Carslaw, Kenneth S.

AU - Kulmala, Markku

AU - Curtius, Joachim

AU - Baltensperger, Urs

AU - Worsnop, Douglas R.

AU - Vehkamaki, Hanna

AU - Kirkby, Jasper

PY - 2013/10/17

Y1 - 2013/10/17

N2 - Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei1. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes2. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases2. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere3. It is thought that amines may enhance nucleation4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.

AB - Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei1. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes2. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases2. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere3. It is thought that amines may enhance nucleation4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.

KW - IONIZATION MASS-SPECTROMETRY

KW - FORMATION EVENTS

KW - AEROSOL NUCLEATION

KW - ALIPHATIC-AMINES

KW - BOREAL FOREST

KW - AMMONIA

KW - NANOPARTICLES

KW - DIMETHYLAMINE

KW - RATES

KW - WATER

U2 - 10.1038/nature12663

DO - 10.1038/nature12663

M3 - Article

SN - 0028-0836

VL - 502

SP - 359

EP - 363

JO - Nature

JF - Nature

IS - 7471

ER -

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

Abstract

Funding

UN SDGs

Austrian Fields of Science 2012

Keywords

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