Date of Award

Summer 9-2017

Embargo Period

3-28-2018

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Civil and Environmental Engineering

Advisor(s)

Ryan Sullivan

Second Advisor

Neil Donahue

Abstract

I advanced the understanding of particle morphology and its implications for the behavior and effects of atmospheric aerosol particles. I have developed new experimental methods for the Aerosol Optical Tweezers (AOT) system and expanded the AOT’s application into studying realistic secondary organic aerosol (SOA) particle phases. The AOT is a highly accurate system developed to study individual particles in real-time for prolonged periods of time. While previous AOT studies have focused on binary or ternary chemical systems, I have investigated complex SOA, and how they interact with other chemical phases, and the surrounding gas-phase. This work has led to new insights into liquid-liquid phase separation and the resulting particle morphology, the surface tension, solubility, and volatility of SOA, and diffusion coefficients of SOA phases. I designed a new aerosol optical tweezers chamber for delivering a uniformly mixed aerosol flow to the trapped droplet’s position. I used this chamber to determine the phase-separation morphology and resulting properties of complex mixed droplets. A series of experiments using simple compounds are presented to establish my ability to use the cavity enhanced Raman spectra to distinguish between homogenous single-phase, and phase-separated core-shell or partially-engulfed morphologies. I have developed a new algorithm for the analysis of whispering gallery modes (WGMs) present in the cavity enhanced Raman spectra retrieved from droplets trapped in the AOT. My algorithm improves the computational scaling when analyzing core-shell droplets (i.e. phase-separated or biphasic droplets) in the AOT, making it computationally practical to analyze spectra collected over many hours at a few Hz. I then demonstrate for the first time the capture and analysis of SOA on a droplet suspended in an AOT. I examined three initial chemical systems of aqueous NaCl, aqueous glycerol, and squalane at ~ 75% relative humidity. For each system I added α-pinene SOA – generated directly in the AOT chamber – to the trapped droplet. The resulting morphology was always observed to be a core of the initial droplet surrounded by a shell of the added SOA. By combining my AOT observations of particle morphology with results from SOA smog chamber experiments, I conclude that the α-pinene SOA shell creates no major diffusion limitations for water, glycerol, and squalane under humid conditions. My AOT experiments highlight the prominence of phase-separated core-shell morphologies for secondary organic aerosols interacting with a range of other chemical phases. The unique analytical capabilities of the aerosol optical tweezers provide a new approach for advancing the understanding of the chemical and physical evolution of complex atmospheric particulate matter, and the important environmental impacts of aerosols on atmospheric chemistry, air quality, human health, and climate change.

Available for download on Wednesday, March 28, 2018

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