Size-Dependent Morphology, Composition, Phase State, and Water Uptake of Nascent Submicrometer Sea Spray Aerosols during a Phytoplankton Bloom

The impact of sea spray aerosols (SSAs) on Earth's climate remains uncertain in part due to size-dependent particle-to-particle variability in SSA physicochemical properties such as morphology, composition, phase state, and water uptake that can be further modulated by the environment relative humidity (RH). The current study investigates these properties as a function of particle size and RH, while focusing on submicrometer nascent SSA (0.1-0.6 mu m) collected throughout a phytoplankton bloom. Filter-based thermal optical analysis, atomic force microscopy (AFM), and AFM photothermal infrared spectroscopy (AFM-PTIR) were utilized in this regard. AFM imaging at 20% RH identified five main SSA morphologies: prism-like, core-shell, rounded, rod, and aggregate. The majority of smaller SSAs throughout a bloom were rounded, while larger SSAs were core-shell. Filter-based measurements revealed an increasing organic mass fraction with decreasing SSA size. The organic matter is shown to primarily reside in a rounded and core-shell SSA, while the prism-like and rod SSA are predominantly inorganic salts (i.e., sodium chloride, nitrates, and sulfates) with relatively low organic content, as determined by AFM-PTIR spectroscopy. AFM phase state measurements at 20% RH revealed an increasing abundance of core-shell SSA with semisolid shells and rounded SSA with a solid phase state, as the particle size decreases. At 60% RH, shells of core-shell and rounded SSA uptake water, become less viscous, and their phase states change into either semisolid or liquid. Collectively, findings reveal the dynamic and size-dependent nature of SSA's morphology, composition, phase states, and water uptake, which should be considered to accurately predict their climate-related effects.