Articles | Volume 16, issue 20
Atmos. Chem. Phys., 16, 12945–12959, 2016
Atmos. Chem. Phys., 16, 12945–12959, 2016

Research article 19 Oct 2016

Research article | 19 Oct 2016

A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio

Xuan Zhang1, Jordan E. Krechmer2,3, Michael Groessl4, Wen Xu1, Stephan Graf4, Michael Cubison4, John T. Jayne1, Jose L. Jimenez2,3, Douglas R. Worsnop1, and Manjula R. Canagaratna1 Xuan Zhang et al.
  • 1Center for Aerosol and Cloud Chemistry, Aerodyne Research Inc., Billerica, MA 01821, USA
  • 2Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA
  • 3Cooperative Institute for Research in Environmental Sciences, Boulder, CO 80309, USA
  • 4TOFWERK, 3600 Thun, Switzerland

Abstract. A new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio (mz), a two-dimensional Ω − mz space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω − mz space. Species of the same chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω − mz space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.

Short summary
We develop a novel two-dimensional space to probe the molecular composition of atmospheric organic aerosols.
Final-revised paper