ABSTRACT
This article summarizes and compares the analysis of the surfaces of natural aerosol particles from three different forest environments by vibrational sum frequency generation. The experiments were carried out directly on filter and impactor substrates, without the need for sample preconcentration, manipulation, or destruction. We discuss the important first steps leading to secondary organic aerosol (SOA) particle nucleation and growth from terpene oxidation by showing that, as viewed by coherent vibrational spectroscopy, the chemical composition of the surface region of aerosol particles having sizes of 1 µm and lower appears to be close to size-invariant. We also discuss the concept of molecular chirality as a chemical marker that could be useful for quantifying how chemical constituents in the SOA gas phase and the SOA particle phase are related in time. Finally, we describe how the combination of multiple disciplines, such as aerosol science, advanced vibrational spectroscopy, meteorology, and chemistry can be highly informative when studying particles collected during atmospheric chemistry field campaigns, such as those carried out during HUMPPA-COPEC-2010, AMAZE-08, or BEARPEX-2009, and when they are compared to results from synthetic model systems such as particles from the Harvard Environmental Chamber (HEC). Discussions regarding the future of SOA chemical analysis approaches are given in the context of providing a path toward detailed spectroscopic assignments of SOA particle precursors and constituents and to fast-forward, in terms of mechanistic studies, through the SOA particle formation process.
