Journal Article

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

Ehrhart, Sebastian, Schobesberger, Siegfried, Curtius, Joachim, Petäjä, Tuukka, Dommen, Josef, Kirkby, Jasper, Ye, Penglin, Worsnop, Douglas R., Breitenlechner, Martin, Praplan, Arnaud P., Sipilä, Mikko, Onnela, Antti, Seinfeld, John H., Wimmer, Daniela, Baltensperger, Urs, Steiner, Gerhard, Tröstl, Jasmin, Carslaw, Kenneth S., Sarnela, Nina, Lehtipalo, Katrianne, Flagan, Richard C., Hakala, Jani, Tomé, António, Kangasluoma, Juha, Adamov, Alexey, Almeida, João, Kürten, Andreas, Amorim, Antonio, Hansel, Armin, Simon, Mario, Heinritzi, Martin, Junninen, Heikki, Leiminger, Markus, Mathot, Serge, Makhmutov, Vladimir, Duplissy, Jonathan, Franchin, Alessandro, Rissanen, Matti P., Rondo, Linda, Bianchi, Federico, Riccobono, Francesco, Williamson, Christina, Donahue, Neil M., Jokinen, Tuija, Kulmala, Markku, Laaksonen, Ari, Winkler, Paul M., Hutterli, Manuel

2014

Overview

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. Significance A significant fraction of atmospheric aerosols is formed from the condensation of low-volatility vapors. These newly formed particles can grow, become seeds for cloud particles, and influence climate. New particle formation in the planetary boundary layer generally proceeds via the neutral channel. However, unambiguous identification of neutral nucleating clusters has so far not been possible under atmospherically relevant conditions. We explored the system of sulfuric acid, water, and dimethylamine in a well-controlled laboratory experiment and measured the time-resolved concentrations of neutral clusters. Clusters containing up to 14 sulfuric acid and 16 dimethylamine molecules were observed. Our results demonstrate that a cluster containing as few as two sulfuric acid and one or two dimethylamine molecules is already stable against evaporation.

• Publisher: National Academy of Sciences
• Subject: Aerosols / Amines / Atmospheric aerosols / Atmospherics / Boundary layer / Boundary layers / Climate / Composite particles / Dimers / dimethylamine / Environmental Sciences / Evaporation / Instrumentation / Kinetics / Molecules / Neutral particles / Nucleation / Physical Sciences / seeds / Sulfuric acid / Sulfuric acids / vapors