Liquid-Liquid Phase Separation of Atmospheric Aerosols: Effect of Oxygen to Carbon Ratios on Dynamics of Partitioning

NATHAN EDDINGSAAS, Jay Denison, Rochester Institute of Technology

     Abstract Number: 581
     Working Group: Aerosol Chemistry

Abstract
Atmospheric aerosols consisting of organic and inorganic components may undergo liquid-liquid phase separation (LLPS) under ambient relative humidities. A typical LLPS structure consists of an organic shell surrounding an inorganic core. Literature states that LLPS occurs when the ratio of oxygen to carbon (O:C) of the organic components is between ~0.56 and ~0.71. Majority of studies look at systems of one organic and inorganic component, and those which study multiple organic components focus on the average O:C ratio of the system to determine if LLPS occurs. Using optical and Raman microscopy, we studied how the composition of each phase changes as the ratio of organic components and average O:C ratio fluctuates.  


Individual aerosol droplets (25 – 300 µm) containing ammonium sulfate, polyethylene glycol (PEG) (O:C 0.56), and sorbitol (O:C 1.0) were placed on a hydrophobically coated slide. The ratio of PEG to sorbitol was varied to stay within an average O:C ratio of 0.56-0.71. For optical microscopy, the slide was placed in a flow cell with a humidity generator, and the radii of the core and shell were measured, as a function of ratio of PEG to sorbitol. For Raman microscopy, the slide was placed in a closed cell containing a saturated salt solution to obtain the desired relative humidity, and spectra were recorded in a 20x20 grid mapped the entire droplet.


LLPS only occurred when the average O:C ratio was between 0.56 and 0.71; however, the O:C ratio of the individual organic molecules determined where it resided during phase separation: lower O:C in the shell, higher O:C in the core with the ammonium sulfate. This result shows that there is not necessarily a strict separation between organic and inorganic species during LLPS.