Effects of Wind Speed on Size-Dependent Morphology and Composition of Sea Spray Aerosols.

Variable wind speeds over the ocean can have a significant impact on the formation mechanism and physical-chemical properties of sea spray aerosols (SSA), which in turn influence their climate-relevant impacts. Herein, for the first time, we investigate the effects of wind speed on size-dependent morphology and composition of individual nascent SSA generated from wind-wave interactions of natural seawater within a wind-wave channel as a function of size and their particle-to-particle variability. Filter-based thermal optical analysis, atomic force microscopy (AFM), AFM infrared spectroscopy (AFM-IR), and scanning electron microscopy (SEM) were employed in this regard. This study focuses on SSA with sizes within 0.04-1.8 µm generated at two wind speeds: 10 m/s, representing a wind lull scenario over the ocean, and 19 m/s, indicative of the wind speeds encountered in stormy conditions. Filter-based measurements revealed a reduction of the organic mass fraction as the wind speed increases. AFM imaging at 20% relative humidity of individual SSA identified six main morphologies: prism-like, rounded, core-shell, rod, rod inclusion core-shell, and aggregates. At 10 m/s, most SSA were rounded, while at 19 m/s, core-shells became predominant. Based on AFM-IR, rounded SSA at both wind speeds had similar composition, mainly composed of aliphatic and oxygenated species, whereas the shells of core-shells displayed more oxygenated organics at 19 m/s and more aliphatic organics at 10 m/s. Collectively, our observations can be attributed to the disruption of the sea surface microlayer film structure at higher wind speeds. The findings reveal a significant impact of wind speed on morphology and composition of SSA, which should be accounted for accurate assessment of their climate effects.

Quantifying the Viscosity of Individual Submicrometer Semisolid Particles Using Atomic Force Microscopy.

Atmospheric aerosols' viscosities can vary significantly depending on their composition, mixing states, relative humidity (RH) and temperature. The diffusion time scale of atmospheric gases into an aerosol is largely governed by its viscosity, which in turn influences heterogeneous chemistry and climate-relevant aerosol effects. Quantifying the viscosity of aerosols in the semisolid phase state is particularly important as they are prevalent in the atmosphere and have a wide range of viscosities. Currently, direct viscosity measurements of submicrometer individual atmospheric aerosols are limited, largely due to the inherent size limitations of existing experimental techniques. Herein, we present a method that utilizes atomic force microscopy (AFM) to directly quantify the viscosity of substrate-deposited individual submicrometer semisolid aerosol particles as a function of RH. The method is based on AFM force spectroscopy measurements coupled with the Kelvin-Voigt viscoelastic model. Using glucose, sucrose, and raffinose as model systems, we demonstrate the accuracy of the AFM method within the viscosity range of ∼104-107 Pa s. The method is applicable to individual particles with sizes ranging from tens of nanometers to several micrometers. Furthermore, the method does not require prior knowledge on the composition of studied particles. We anticipate future measurements utilizing the AFM method on atmospheric aerosols at various RH to aid in our understanding of the range of aerosols' viscosities, the extent of particle-to-particle viscosity variability, and how these contribute to the particle diversity observable in the atmosphere.

Effects of Atmospheric Aging Processes on Nascent Sea Spray Aerosol Physicochemical Properties.

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.

Probing the Water Uptake and Phase State of Individual Sucrose Nanoparticles Using Atomic Force Microscopy.

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 1011.2 and 102.5 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.