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Neutral molecular cluster formation of sulfuric acid–dimethylamine observed in real time under atmospheric conditions

Kürten, Andreas and Flagan, Richard C. and Seinfeld, John H. (2014) Neutral molecular cluster formation of sulfuric acid–dimethylamine observed in real time under atmospheric conditions. Proceedings of the National Academy of Sciences of the United States of America, 111 (42). pp. 15019-15024. ISSN 0027-8424. PMCID PMC4210346. http://resolver.caltech.edu/CaltechAUTHORS:20141015-092611684

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Abstract

For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1073/pnas.1404853111DOIArticle
http://www.pnas.org/content/111/42/15019.abstractPublisherArticle
http://www.pnas.org/lookup/suppl/doi:10.1073/pnas.1404853111/-/DCSupplementalPublisherSupporting Information
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4210346/PubMed CentralArticle
ORCID:
AuthorORCID
Flagan, Richard C.0000-0001-5690-770X
Additional Information:© 2014 National Academy of Sciences. Freely available online through the PNAS open access option. Edited by Barbara J. Finlayson-Pitts, University of California, Irvine, CA, and approved September 8, 2014 (received for review March 21, 2014). We thank the European Center for Nuclear Research (CERN) for supporting Cosmics Leaving Outdoor Droplets (CLOUD) with important technical and financial resources and for providing a particle beam from the CERN Proton Synchrotron. We also thank P. Carrie, L.-P. De Menezes, J. Dumollard, K. Ivanova, F. Josa, I. Krasin, R. Kristic, A. Laassiri, O. S. Maksumov, B. Marichy, H. Martinati, S. V. Mizin, R. Sitals, A. Wasem, and M. Wilhelmsson for their important contributions to the experiment and P. H. McMurry for helpful discussion. We thank the tofTools team for providing tools for mass spectrometry analysis. This research has received funding from the European Commission Seventh Framework Programme (Marie Curie Initial Training Network “CLOUD-ITN” 215072, MC-ITN “CLOUD-TRAIN” 316662, European Research Council (ERC)-Starting “MOCAPAF” Grant 57360, and ERC-Advanced “ATMNUCLE” Grant 227463). This research has also received funding from the German Federal Ministry of Education and Research (Projects 01LK0902A and 01LK1222A), the Swiss National Science Foundation (Projects 200020 135307 and 206620 141278), the Academy of Finland (135054, 133872, 251427, 139656, 139995, 137749, 141217, 141451 and Center of Excellence Project 1118615), the Finnish Funding Agency for Technology and Innovation, the Väisälä Foundation, the Nessling Foundation, the Austrian Science Fund (Project J3198-N21), the Portuguese Foundation for Science and Technology (Project CERN/FP/116387/2010), the Swedish Research Council, Vetenskapsrå̊det (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), the US National Science Foundation (Grants AGS1136479 and CHE1012293), Pan-European Gas-Aerosols-Climate Interaction Study project [funded by the European Commission under the Framework Program 7 (FP7-ENV-2010-265148)], and the Davidow Foundation.
Funders:
Funding AgencyGrant Number
European Center for Nuclear ResearchUNSPECIFIED
Marie Curie Initial Training Network215072
Marie Curie Initial Training Network316662
European Research Council (ERC)57360
European Research Council (ERC)227463
Bundesministeriums für Bildung und Forschung (BMBF)01LK0902A
Bundesministeriums für Bildung und Forschung (BMBF)01LK1222A
Swiss National Science Foundation (SNSF)200020
Swiss National Science Foundation (SNSF)135307
Swiss National Science Foundation (SNSF)206620 141278
Academy of Finland135054
Academy of Finland133872
Academy of Finland251427
Academy of Finland139656
Academy of Finland139995
Academy of Finland137749
Academy of Finland141217
Academy of Finland141451
Academy of Finland1118615
Finnish Funding Agency for Technology and InnovationUNSPECIFIED
Väisälä FoundationUNSPECIFIED
Nessling FoundationUNSPECIFIED
FWF Der WissenschaftsfondsJ3198-N21
Fundação para a Ciência e a Tecnologia (FCT)CERN/FP/116387/2010
Swedish Research Council12-02-91522-CERN
NSFAGS1136479
NSFCHE1012293
Pan-European Gas-Aerosols-Climate Interaction Study projectFP7-ENV-2010-265148
Davidow FoundationUNSPECIFIED
Subject Keywords:aerosol particles; atmospheric nucleation; atmospheric chemistry; mass spectrometry
PubMed Central ID:PMC4210346
Record Number:CaltechAUTHORS:20141015-092611684
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20141015-092611684
Official Citation:Andreas Kürten, Tuija Jokinen, Mario Simon, Mikko Sipilä, Nina Sarnela, Heikki Junninen, Alexey Adamov, João Almeida, Antonio Amorim, Federico Bianchi, Martin Breitenlechner, Josef Dommen, Neil M. Donahue, Jonathan Duplissy, Sebastian Ehrhart, Richard C. Flagan, Alessandro Franchin, Jani Hakala, Armin Hansel, Martin Heinritzi, Manuel Hutterli, Juha Kangasluoma, Jasper Kirkby, Ari Laaksonen, Katrianne Lehtipalo, Markus Leiminger, Vladimir Makhmutov, Serge Mathot, Antti Onnela, Tuukka Petäjä, Arnaud P. Praplan, Francesco Riccobono, Matti P. Rissanen, Linda Rondo, Siegfried Schobesberger, John H. Seinfeld, Gerhard Steiner, António Tomé, Jasmin Tröstl, Paul M. Winkler, Christina Williamson, Daniela Wimmer, Penglin Ye, Urs Baltensperger, Kenneth S. Carslaw, Markku Kulmala, Douglas R. Worsnop, and Joachim Curtius Neutral molecular cluster formation of sulfuric acid–dimethylamine observed in real time under atmospheric conditions PNAS 2014 111 (42) 15019-15024; published ahead of print October 6, 2014, doi:10.1073/pnas.1404853111
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:50395
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:15 Oct 2014 22:54
Last Modified:13 Apr 2016 21:49

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