ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-4319-2011 Size distribution of alkyl amines in continental particulate matter and their online detection in the gas and particle phase VandenBoer T. C. 1 Petroff A. 1 Markovic M. Z. 1 Murphy J. G. 1 Department of Chemistry, University of Toronto, Toronto, Canada 10 05 2011 11 9 4319 4332 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/11/4319/2011/acp-11-4319-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/4319/2011/acp-11-4319-2011.pdf

An ion chromatographic method is described for the quantification of the simple alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA) and triethylamine (TEA), in the ambient atmosphere. Limits of detection (3σ) are in the tens of pmol range for all of these amines, and good resolution is achieved for all compounds except for TMA and DEA. The technique was applied to the analysis of time-integrated samples collected using a micro-orifice uniform deposition impactor (MOUDI) with ten stages for size resolution of particles with aerodynamic diameters between 56 nm and 18 μm. In eight samples from urban and rural continental airmasses, the mass loading of amines consistently maximized on the stage corresponding to particles with aerodynamic diameters between 320 and 560 nm. The molar ratio of amines to ammonium (R<sub>3</sub>NH<sup>+</sup>/NH<sub>4</sub><sup>+</sup>) in fine aerosol ranged between 0.005 and 0.2, and maximized for the smallest particle sizes. The size-dependence of the R<sub>3</sub>NH<sup>+</sup>/NH<sub>4</sub><sup>+</sup> ratio indicates differences in the relative importance of the processes leading to the incorporation of amines and ammonia into secondary particles. The technique was also used to make simultaneous hourly online measurements of amines in the gas phase and in fine particulate matter using an Ambient Ion Monitor Ion Chromatograph (AIM-IC). During a ten day campaign in downtown Toronto, DMA, TMA + DEA, and TEA were observed to range from below detection limit to 2.7 ppt in the gas phase. In the particle phase, MAH<sup>+</sup> and TMAH<sup>+</sup> + DEAH<sup>+</sup> were observed to range from below detection limit up to 15 ng m<sup>−3</sup>. The presence of detectable levels of amines in the particle phase corresponded to periods with higher relative humidity and higher mass loadings of nitrate. While the hourly measurements made using the AIM-IC provide data that can be used to evaluate the application of gas-particle partitioning models to amines, the strong size-dependence of the R<sub>3</sub>NH<sup>+</sup>/NH<sub>4</sub><sup>+</sup> ratio indicates that using bulk measurements may not be appropriate.

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