Probing surfaces of atmospherically relevant organic particles by easy ambient sonic-spray ionization mass spectrometry (EASI-MS)

Both ambient and laboratory-generated particles can have a surface composition different from the bulk, but there are currently few analytical techniques available to probe these differences. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) was applied to solid, laboratory-generated particles with core–shell morphologies formed from a variety of dicarboxylic acids. The soft ionization facilitated parent peak detection for the two compounds, from which the depth probed could be determined from the relative signal intensities. Two different configurations of a custom-made nebulizer are reported that yield different probe depths. In the “orthogonal mode,” with the nebulizer ∼10 centimeters away from the particle stream and at a 90° angle to the MS inlet, evaporation of the nebulizer droplets forms ions before interaction with the particles. The probe depth for orthogonal mode EASI-MS is shown to be 2–4 nm in these particle systems. In the “droplet mode”, the nebulizer and particle streams are in close proximity to each other and the MS inlet so that the particles interact with charged liquid droplets. This configuration resulted in full dissolution of the particles and gives particle composition similar to that from collection on filters and extraction of the particles (bulk). These studies establish that EASI-MS is a promising technique for probing the chemical structures of inhomogeneous airborne organic particles.