Hygroscopic Growth, Phase Morphology, and Optical Properties of Model Aqueous Brown Carbon Aerosol

Brown carbon aerosol in the atmosphere contain light-absorbing chromophores that influence the optical scattering properties of the particles. These chromophores may be hydrophobic, such as PAHs, or water soluble, such as nitroaromatics, imidazoles, and other conjugated oxygen-rich molecules. Water-soluble chromophores are expected to exist in aqueous solution in the presence of sufficient water and will exhibit physical properties (e.g., size, refractive index, and phase morphology) that depend on the environmental relative humidity (RH). In this work, we characterize the RH-dependent properties of 4-nitrocatechol (4-NC) and its mixtures with ammonium sulfate, utilizing a single-particle levitation platform coupled with Mie resonance spectroscopy to probe the size, real part of the complex refractive index (RI), and phase morphology of individual micron-sized particles. We measure the hygroscopic growth properties of pure 4-NC and apply mixing rules to characterize the growth of mixtures with ammonium sulfate. We report the RI at 589 nm for these samples as a function of RH and explore the wavelength dependence of the RI at non-absorbing wavelengths. The real part of the RI at 589 nm was found to vary in the range 1.54-1.59 for pure 4-NC from 92.5 to 75% RH, with an estimated pure component RI of 1.70. The real part of the RI was also measured for mixtures of AS and 4-NC and ranged from 1.39 to 1.51 depending on the component ratio and RH. We went on to characterize phase transitions in mixed particles, identifying the onset RH of liquid-liquid phase separation (LLPS) and efflorescence transitions. Mixtures showed LLPS in the range of 85-76% RH depending on the molar ratio, while efflorescence typically fell between 22 and 42% RH. Finally, we characterized the imaginary part of the complex RI using an effective oscillator model to capture the wavelength-dependent absorption properties of the system.