Online laser desorption-multiphoton postionization mass spectrometry of individual aerosol particles: molecular source indicators for particles emitted from different traffic-related and wood combustion sources.

Direct inlet aerosol mass spectrometry plays an increasingly important role in applied and fundamental aerosol and nanoparticle research. Laser desorption/ionization (LDI) based techniques for single particle time-of-flight mass spectrometry (LDI-SP-TOFMS) are a promising approach in the chemical analysis of single aerosol particles, especially for the detection of inorganic species and distinction of particle classes. However, until now the detection of molecular organic compounds on a single particle basis has been difficult due to the high laser power densities which are required for the LDI process as well as due to the inherent matrix effects associated with this ionization technique. By the application of a two-step approach, where an IR desorption laser pulse is applied to perform a gentle desorption of organic material from the single particle surface and a second UV-laser performs the soft ionization of the desorbed species, this drawback of laser based single particles mass spectrometry can be overcome. The postionization of the desorbed molecules has been accomplished in this work by resonance enhanced multiphoton ionization (REMPI) using a KrF excimer laser (248 nm). REMPI allows an almost fragmentation free trace analysis of polycyclic aromatic hydrocarbons (PAHs) and their derivatives from individual single particles (laser desorption-REMPI postionization-single particle-time-of-flight mass spectrometry or LD-REMPI-SP-TOFMS). Crucial system parameters of the home-built aerosol mass spectrometer such as the power densities and the relative timing of both lasers were optimized with respect to the detectability of particle source specific organic signatures using well characterized standard particles. In a second step, the LD-REMPI-SP-TOFMS system was applied to analyze different real world aerosols (spruce wood combustion, gasoline car exhaust, beech wood combustion, and diesel car exhaust). It was possible to distinguish the particles from different sources by their molecular signature. Finally, exemplary ambient aerosol measurements have been carried out, which demonstrate the potential of the method for investigating urban aerosol and making contributions to source attribution studies.