Articles | Volume 16, issue 19
Atmos. Chem. Phys., 16, 12513–12529, 2016
Atmos. Chem. Phys., 16, 12513–12529, 2016

Research article 07 Oct 2016

Research article | 07 Oct 2016

Chemical ionization of clusters formed from sulfuric acid and dimethylamine or diamines

Coty N. Jen1,a, Jun Zhao1,b, Peter H. McMurry1, and David R. Hanson2 Coty N. Jen et al.
  • 1Department of Mechanical Engineering, University of Minnesota, Twin Cities, 111 Church St. SE, Minneapolis, MN 55455, USA
  • 2Department of Chemistry, Augsburg College, 2211 Riverside Ave., Minneapolis, MN 55454, USA
  • anow at: Department of Environmental Science, Policy, and Management, University of California, Berkeley, Hilgard Hall, Berkeley, CA 94720, USA
  • bnow at: Institute of Earth Climate and Environment System, Sun Yat-sen University, 135 West Xingang Road, 510275 Guangzhou, China

Abstract. Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to deprotonate and thus chemically ionize the clusters. In this study, we compare cluster concentrations measured using either nitrate or acetate. Clusters were formed in a flow reactor from vapors of sulfuric acid and dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine). These comparisons show that nitrate is unable to chemically ionize clusters with high base content. In addition, we vary the ion–molecule reaction time to probe ion processes which include proton-transfer, ion–molecule clustering, and decomposition of ions. Ion decomposition upon deprotonation by acetate/nitrate was observed. More studies are needed to quantify to what extent ion decomposition affects observed cluster content and concentrations, especially those chemically ionized with acetate since it deprotonates more types of clusters than nitrate.

Model calculations of the neutral and ion cluster formation pathways are also presented to better identify the cluster types that are not efficiently deprotonated by nitrate. Comparison of model and measured clusters indicate that sulfuric acid dimers with two diamines and sulfuric acid trimers with two or more base molecules are not efficiently chemical ionized by nitrate. We conclude that acetate CI provides better information on cluster abundancies and their base content than nitrate CI.

Short summary
Chemical ionization mass spectrometry measurements of clusters formed from sulfuric acid and dimethylamine or various diamines show that these clusters are not as efficiently ionized by nitrate as they are by acetate. These clusters are atmospherically relevant, and our results suggest that traditional methods may under-measure cluster concentrations by up to a factor of 10.
Final-revised paper