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Title: Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD

New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH 3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneousmore » conversion of SO 2 to sulfate. Furthermore, these results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4] ; ORCiD logo [5] ;  [6] ;  [7] ;  [8] ;  [9] ; ORCiD logo [10] ;  [10] ;  [11] ;  [10] ;  [12] ;  [13] ;  [11] ; ORCiD logo [10] ;  [10] ;  [8] ;  [8] more »;  [10] ;  [14] ;  [15] ;  [4] ;  [2] ;  [16] « less
  1. Univ. of California, Irvine, CA (United States); National Center for Atmospheric Research, Boulder, CO (United States); Univ. of Eastern Finland, Kuopio (Finland)
  2. Univ. of Vienna, Vienna (Austria)
  3. Univ. of Eastern Finland, Kuopio (Finland); Korea Polar Research Institute, Incheon (Republic of Korea)
  4. Stockholm Univ., Stockholm (Sweden)
  5. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  6. Univ. of Helsinki, Helsinki (Finland); Finnish Meteorological Institute, Helsinki (Finland)
  7. Univ. of Helsinki, Helsinki (Finland); Univ. of Washington, Seattle, WA (United States)
  8. Goethe Univ. of Frankfurt, Frankfurt am Main (Germany)
  9. Goethe Univ. of Frankfurt, Frankfurt am Main (Germany); European Organization for Nuclear Research (CERN), Geneva (Switzerland)
  10. Univ. of Helsinki, Helsinki (Finland)
  11. Univ. of Innsbruck, Innsbruck (Austria)
  12. Univ. of Eastern Finland, Kuopio (Finland); Univ. of Helsinki, Helsinki (Finland)
  13. Univ. of Helsinki, Helsinki (Finland); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  14. Goethe Univ. of Frankfurt, Frankfurt am Main (Germany); Univ. of Colorado, Boulder, CO (United States); NOAA Earth System Research Lab., Boulder, CO (United States)
  15. Univ. of Helsinki, Helsinki (Finland); Goethe Univ. of Frankfurt, Frankfurt am Main (Germany)
  16. Univ. of California, Irvine, CA (United States); Univ. of Eastern Finland, Kuopio (Finland)
Publication Date:
Grant/Contract Number:
SC0014469
Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 16; Journal Issue: 21; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Research Org:
Univ. of California, Irvine, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES
OSTI Identifier:
1364419

Lawler, Michael J., Winkler, Paul M., Kim, Jaeseok, Ahlm, Lars, Trostl, Jasmin, Praplan, Arnaud P., Schobesberger, Siegfried, Kurten, Andreas, Kirkby, Jasper, Bianchi, Federico, Duplissy, Jonathan, Hansel, Armin, Jokinen, Tuija, Keskinen, Helmi, Lehtipalo, Katrianne, Leiminger, Markus, Petaja, Tuukka, Rissanen, Matti, Rondo, Linda, Simon, Mario, Sipila, Mikko, Williamson, Christina, Wimmer, Daniela, Riipinen, Ilona, Virtanen, Annele, and Smith, James N.. Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD. United States: N. p., Web. doi:10.5194/acp-16-13601-2016.
Lawler, Michael J., Winkler, Paul M., Kim, Jaeseok, Ahlm, Lars, Trostl, Jasmin, Praplan, Arnaud P., Schobesberger, Siegfried, Kurten, Andreas, Kirkby, Jasper, Bianchi, Federico, Duplissy, Jonathan, Hansel, Armin, Jokinen, Tuija, Keskinen, Helmi, Lehtipalo, Katrianne, Leiminger, Markus, Petaja, Tuukka, Rissanen, Matti, Rondo, Linda, Simon, Mario, Sipila, Mikko, Williamson, Christina, Wimmer, Daniela, Riipinen, Ilona, Virtanen, Annele, & Smith, James N.. Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD. United States. doi:10.5194/acp-16-13601-2016.
Lawler, Michael J., Winkler, Paul M., Kim, Jaeseok, Ahlm, Lars, Trostl, Jasmin, Praplan, Arnaud P., Schobesberger, Siegfried, Kurten, Andreas, Kirkby, Jasper, Bianchi, Federico, Duplissy, Jonathan, Hansel, Armin, Jokinen, Tuija, Keskinen, Helmi, Lehtipalo, Katrianne, Leiminger, Markus, Petaja, Tuukka, Rissanen, Matti, Rondo, Linda, Simon, Mario, Sipila, Mikko, Williamson, Christina, Wimmer, Daniela, Riipinen, Ilona, Virtanen, Annele, and Smith, James N.. 2016. "Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD". United States. doi:10.5194/acp-16-13601-2016. https://www.osti.gov/servlets/purl/1364419.
@article{osti_1364419,
title = {Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD},
author = {Lawler, Michael J. and Winkler, Paul M. and Kim, Jaeseok and Ahlm, Lars and Trostl, Jasmin and Praplan, Arnaud P. and Schobesberger, Siegfried and Kurten, Andreas and Kirkby, Jasper and Bianchi, Federico and Duplissy, Jonathan and Hansel, Armin and Jokinen, Tuija and Keskinen, Helmi and Lehtipalo, Katrianne and Leiminger, Markus and Petaja, Tuukka and Rissanen, Matti and Rondo, Linda and Simon, Mario and Sipila, Mikko and Williamson, Christina and Wimmer, Daniela and Riipinen, Ilona and Virtanen, Annele and Smith, James N.},
abstractNote = {New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. Furthermore, these results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.},
doi = {10.5194/acp-16-13601-2016},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 21,
volume = 16,
place = {United States},
year = {2016},
month = {11}
}