Abstract

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.

Highlights

  • Exploring the physical−chemical properties of atmospheric aerosols is important because they play a major role in regulating climate-relevant processes.[1−7] Aerosols can have direct and indirect effects on the climate, leading to radiative forcing.[6]

  • The direct aerosol effect refers to the ability to scatter and absorb solar radiation, while the indirect effect refers to the aerosols acting as cloud condensation nuclei (CCN) or ice nucleating particles (INPs), facilitating cloud formation.[6,8−11]

  • The 3D growth factors (GFs) was quantified over each individual nanoparticle at a particular relative humidity (RH) value ranging from 7 to 60%, which is defined as the ratio of Dvol at the corresponding RH over that at 7% RH

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Summary

■ INTRODUCTION

Exploring the physical−chemical properties of atmospheric aerosols is important because they play a major role in regulating climate-relevant processes.[1−7] Aerosols can have direct and indirect effects on the climate, leading to radiative forcing.[6]. We previously reported a new method that permits accurate determination of the water uptake and phase state of individual substrate-deposited sub-micrometer aerosols as a function of RH using atomic force microscopy (AFM) imaging and force spectroscopy.[57,64,65] By varying RH, solid, semisolid, and liquid phase states were directly probed for these sub-micrometer aerosols. By employing contact mode AFM force spectroscopy, the solid, semisolid, and liquid phase states of individual sucrose nanoparticles were identified as a function of RH, extending the previously established AFM methodology from sub-micrometer to include sub-100 nm particle sizes. On the basis of the force plots, the viscoelastic response distance (VRD) and relative indentation depth (RID) values were determined for each nanoparticle at a particular RH, as described previously, with each value reported as an average and one standard deviation.[41,57]

■ RESULTS AND DISCUSSION
■ CONCLUSION
■ ACKNOWLEDGMENTS
■ REFERENCES
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