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

Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD. Lawler, M., J., Winkler, P., M., Kim, J., Ahlm, L., Tröstl, J., Praplan, A., P., Schobesberger, S., Kürten, A., Kirkby, J., Bianchi, F., Duplissy, J., Hansel, A., Jokinen, T., Keskinen, H., Lehtipalo, K., Leiminger, M., Petäjä, T., Rissanen, M., Rondo, L., Simon, M., Sipilä, M., Williamson, C., Wimmer, D., Riipinen, I., Virtanen, A., & Smith, J., N. Atmospheric Chemistry and Physics, 16(21):13601-13618, 11, 2016.

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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 10ĝ€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 10-30ĝ€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 baseĝ€:ĝ€acid ratios lower than 1ĝ€:ĝ€1. The lowest base fractions were found in particles below 15ĝ€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. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10ĝ€nm.

@article{
 title = {Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD},
 type = {article},
 year = {2016},
 pages = {13601-13618},
 volume = {16},
 websites = {http://www.atmos-chem-phys.net/16/13601/2016/},
 month = {11},
 day = {3},
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 abstract = {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 10ĝ€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 10-30ĝ€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 baseĝ€:ĝ€acid ratios lower than 1ĝ€:ĝ€1. The lowest base fractions were found in particles below 15ĝ€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. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10ĝ€nm.},
 bibtype = {article},
 author = {Lawler, Michael J. and Winkler, Paul M. and Kim, Jaeseok and Ahlm, Lars and Tröstl, Jasmin and Praplan, Arnaud P. and Schobesberger, Siegfried and Kürten, 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 Petäjä, Tuukka and Rissanen, Matti and Rondo, Linda and Simon, Mario and Sipilä, Mikko and Williamson, Christina and Wimmer, Daniela and Riipinen, Ilona and Virtanen, Annele and Smith, James N.},
 doi = {10.5194/acp-16-13601-2016},
 journal = {Atmospheric Chemistry and Physics},
 number = {21}
}

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