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Observations of aminium salts in atmospheric nanoparticles and possible climatic implications

Smith, James N., Barsanti, Kelley C., Friedli, Hans R., Ehn, Mikael, Kulmala, Markku, Collins, Donald R., Scheckman, Jacob H., Williams, Brent J., McMurry, Peter H.
Proceedings of the National Academy of Sciences of the United States of America 2010 v.107 no.15 pp. 6634-6639
amines, ammonium sulfate, climate, desorption, hygroscopicity, ionization, ions, models, nanoparticles, organic acids and salts, spectrometers, Colorado, Finland, Mexico
We present laboratory studies and field observations that explore the role of aminium salt formation in atmospheric nanoparticle growth. These measurements were performed using the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) and Ultrafine Hygroscopicity Tandem Differential Mobility Analyzers. Laboratory measurements of alkylammonium--carboxylate salt nanoparticles show that these particles exhibit lower volatilities and only slightly lower hygroscopicities than ammonium sulfate nanoparticles. TDCIMS measurements of these aminium salts showed that the protonated amines underwent minimal decomposition during analysis, with detection sensitivities comparable to those of organic and inorganic deprotonated acids. TDCIMS observations made of a new particle formation event in an urban site in Tecamac, Mexico, clearly indicate the presence of protonated amines in 8-10 nm diameter particles accounting for about 47% of detected positive ions; 13 nm particles were hygroscopic with an average 90% RH growth factor of 1.42. Observations of a new particle formation event in a remote forested site in Hyytiälä, Finland, show the presence of aminium ions with deprotonated organic acids; 23% of the detected positive ions during this event are attributed to aminium salts while 10 nm particles had an average 90% RH growth factor of 1.27. Similar TDCIMS observations during events in Atlanta and in the vicinity of Boulder, Colorado, show that aminium salts accounted for 10-35% of detected positive ions. We conclude that aminium salts contribute significantly to nanoparticle growth and must be accounted for in models to accurately predict the impact of new particle formation on climate.