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 μm) 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.

The effects of atmospheric aerosols on the climate and atmosphere of Earth can vary significantly depending upon their properties, including size, morphology, and phase state, all of which are influenced by varying relative humidity (RH) in the atmosphere. A significant fraction of atmospheric aerosols is below 100 nm in size. However, as a result of size limitations of conventional experimental techniques, how the particle-to-particle variability of the phase state of aerosols influences atmospheric processes is poorly understood. To address this issue, the atomic force microscopy (AFM) methodology that was previously established for sub-micrometer aerosols is extended to measure the water uptake and identify the phase state of individual sucrose nanoparticles. Quantified growth factors (GFs) of individual sucrose nanoparticles up to 60% RH were lower than expected values observed on the sub-micrometer sucrose particles. The effect could be attributed to the semisolid sucrose nanoparticle restructuring on a substrate. At RH > 60%, sucrose nanoparticles are liquid and GFs overlap well with the sub-micrometer particles and theoretical predictions. This suggests that quantification of GFs of nanoparticles may be inaccurate for the RH range where particles are semisolid but becomes accurate at elevated RH where particles are liquid. Despite this, however, the identified phase states of the nanoparticles were comparable to their sub-micrometer counterparts. The identified phase transitions between solid and semisolid and between semisolid and liquid for sucrose were at ∼18 and 60% RH, which are equivalent to viscosities of 10 11.2 and 10 2.5 Pa s, respectively. This work demonstrates that measurements of the phase state using AFM are applicable to nanosized particles, even when the substrate alters the shape of semisolid nanoparticles and alters the GF.

The effects of atmospheric aging on single-particle nascent sea spray aerosol (nSSA) physicochemical properties, such as morphology, composition, phase state, and water uptake, are important to understanding their impacts on the Earth’s climate. The present study investigates these properties by focusing on the aged SSA (size range of 0.1–0.6 μm) and comparing with a similar size range nSSA, both generated at a peak of a phytoplankton bloom during a mesocosm study. The aged SSAs were generated by exposing nSSA to OH radicals with exposures equivalent to 4–5 days of atmospheric aging. Complementary filter-based thermal optical analysis, atomic force microscopy (AFM), and AFM photothermal infrared spectroscopy were utilized. Both nSSA and aged SSA showed an increase in the organic mass fraction with decreasing particle sizes. In addition, aging results in a further increase of the organic mass fraction, which can be attributed to new particle formation and oxidation of volatile organic compounds followed by condensation on pre-existing particles. The results are consistent with single-particle measurements that showed a relative increase in the abundance of aged SSA core–shells with significantly higher organic coating thickness, relative to nSSA. Increased hygroscopicity was observed for aged SSA core–shells, which had more oxygenated organic species. Rounded nSSA and aged SSA had similar hygroscopicity and no apparent changes in the composition. The observed changes in aged SSA physicochemical properties showed a significant size-dependence and particle-to-particle variability. Overall, results showed that the atmospheric aging can significantly influence the nSSA physicochemical properties, thus altering the SSA effects on the climate.