Articles | Volume 7, issue 10
Atmos. Meas. Tech., 7, 3611–3621, 2014
Atmos. Meas. Tech., 7, 3611–3621, 2014

Research article 29 Oct 2014

Research article | 29 Oct 2014

Amine permeation sources characterized with acid neutralization and sensitivities of an amine mass spectrometer

N. A. Freshour, K. K. Carlson, Y. A. Melka, S. Hinz, B. Panta, and D. R. Hanson N. A. Freshour et al.
  • Chemistry Department, Augsburg College, Minneapolis, MN 55454, USA

Abstract. An acid titration method for quantifying amine permeation rates was used to calibrate an Ambient pressure Proton transfer Mass Spectrometer (AmPMS) that monitors ambient amine compounds. The method involves capturing amines entrained in a N2 flow by bubbling it through an acidified solution (~10−5 M HCl), and the amines are quantified via changes in solution pH with time. Home-made permeation tubes had permeation rates (typically tens of pmol s−1) that depended on the type of amine and tubing and on temperature. Calibrations of AmPMS yielded sensitivities for ammonia, methylamine, dimethylamine, and trimethylamine that are close to the sensitivity assuming a gas-kinetic, ion-molecule rate coefficient. The permeation tubes were also designed to deliver a reproducible amount of amine to a flow reactor where nucleation with sulfuric acid was studied. The high proton affinity compound dimethyl sulfoxide (DMSO), linked to oceanic environments, was also studied and AmPMS is highly sensitive to it. AmPMS was deployed recently in two field campaigns and, using these sensitivities, mixing ratios for ammonia and the alkyl amines are derived from the signals. Correlations between these species and with particle formation events are discussed.

Short summary
Amine permeation tubes were quantified via absorption of gaseous amines by dilute acid solutions. Calibrations of an amine mass spectrometer with these permeation tubes show that the mass spectrometer is very sensitive to amines. Measurements of ambient amines are presented from two recent field campaigns. The amine mass spectrometer instrumentation and sampling arrangements are extensively discussed.