Extending surface enhanced Raman spectroscopy (SERS) of atmospheric aerosol particles to the accumulation mode (150-800 nm)Electronic supplementary information (ESI) available. See DOI: 10.1039/c8em00276b

Due to their small size, measurements of the complex composition of atmospheric aerosol particles and their surfaces are analytically challenging. This is particularly true for microspectroscopic methods, where it can be difficult to optically identify individual particles smaller than the diffraction limit of visible light (∼350 nm) and measure their vibrational modes. Recently, surface enhanced Raman spectroscopy (SERS) has been applied to the study of aerosol particles, allowing for detection and characterization of previously undistinguishable vibrational modes. However, atmospheric particles analyzed via SERS have primarily been >1 μm to date, much larger than the diameter of the most abundant atmospheric aerosols (∼100 nm). To push SERS towards more relevant particle sizes, a simplified approach involving Ag foil substrates was developed. Both ambient particles and several laboratory-generated model aerosol systems (polystyrene latex spheres (PSLs), ammonium sulfate, and sodium nitrate) were investigated to determine SERS enhancements. SERS spectra of monodisperse, model aerosols between 400-800 nm were compared with non-SERS enhanced spectra, yielding average enhancement factors of 10 2 for both inorganic and organic vibrational modes. Additionally, SERS-enabled detection of 150 nm size-selected ambient particles represent the smallest individual aerosol particles analyzed by Raman microspectroscopy to date, and the first time atmospheric particles have been measured at sizes approaching the atmospheric number size distribution mode. SERS-enabled detection and identification of vibrational modes in smaller, more atmospherically-relevant particles has the potential to improve understanding of aerosol composition and surface properties, as well as their impact on heterogeneous and multiphase reactions involving aerosol surfaces. Due to their small size, measurements of the complex composition of atmospheric aerosol particles and their surfaces are analytically challenging.