Electrospray surface-enhanced Raman spectroscopy (ES-SERS) for probing surface chemical compositions of atmospherically relevant particles

We present electrospray surface-enhanced Raman spectroscopy (ES-SERS) as a new approach to measuring the surface chemical compositions of atmospherically relevant particles. The surface-sensitive SERS is realized by electrospraying Ag nanoparticle aerosols over analyte particles. Spectral features at v(SO42-), v(C-H) and v(O-H) modes were observed from the normal Raman and SERS measurements of laboratory-generated supermicron particles of ammonium sulfate (AS), AS mixed with succinic acid (AS/SA) and AS mixed with sucrose (AS/sucrose). SERS measurements showed strong interaction (or chemisorption) between Ag nanoparticles and surface aqueous sulfate [SO42-] with [SO42-]AS/sucrose > [SO42-]AS/SA > [SO42-]AS. Enhanced spectra of the solid AS and AS/SA particles revealed the formation of surface-adsorbed water on their surfaces at 60% relative humidity. These observations of surface aqueous sulfate and adsorbed water demonstrate a possible role of surface-adsorbed water in facilitating the dissolution of sulfate from the bulk phase into its water layer(s). Submicron ambient aerosol particles collected in Hong Kong exhibited non-enhanced features of black carbon and enhanced features of sulfate and organic matter (carbonyl group), indicating an enrichment of sulfate and organic matter on the particle surface.