Probing Individual Particles Generated at the Freshwater–Seawater Interface through Combined Raman, Photothermal Infrared, and X-ray Spectroscopic Characterization

[Image: see text] Sea spray aerosol (SSA) is one of the largest global sources of atmospheric aerosol, but little is known about SSA generated in coastal regions with salinity gradients near estuaries and river outflows. SSA particles are chemically complex with substantial particle-to-particle variability due to changes in water temperature, salinity, and biological activity. In previous studies, the ability to resolve the aerosol composition to the level of individual particles has proven necessary for the accurate parameterization of the direct and indirect aerosol effects; therefore, measurements of individual SSA particles are needed for the characterization of this large source of atmospheric aerosol. An integrated analytical measurement approach is required to probe the chemical composition of individual SSA particles. By combining complementary vibrational microspectroscopic (Raman and optical photothermal infrared, O-PTIR) measurements with elemental information from computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM–EDX), we gained unique insights into the individual particle chemical composition and morphology. Herein, we analyzed particles from four experiments on laboratory-based SSA production using coastal seawater collected in January 2018 from the Gulf of Maine. Individual salt particles were enriched in organics compared to that in natural seawater, both with and without added microalgal filtrate, with greater enrichment observed for smaller particle sizes, as evidenced by higher carbon/sodium ratios. Functional group analysis was carried out using the Raman and infrared spectra collected from individual SSA particles. Additionally, the Raman spectra were compared with a library of Raman spectra consisting of marine-derived organic compounds. Saccharides, followed by fatty acids, were the dominant components of the organic coatings surrounding the salt cores of these particles. This combined Raman, infrared, and X-ray spectroscopic approach will enable further understanding of the factors determining the individual particle composition, which is important for understanding the impacts of SSA produced within estuaries and river outflows, as well as areas of snow and ice melt.