Advances in Measurements of the Properties of Aerosol Particles: Acidity, Phase State, and Surface Interactions
Restricted (Penn State Only)
- Author:
- Tackman, Emma
- Graduate Program:
- Chemistry (PHD)
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- February 09, 2023
- Committee Members:
- Jose Fuentes, Outside Unit & Field Member
Miriam Freedman, Chair & Dissertation Advisor
Raymond Schaak, Major Field Member
Lauren Zarzar, Major Field Member
Philip Bevilacqua, Program Head/Chair - Keywords:
- aerosol
microscopy
nanoparticle
acidity
transmission electron microscopy - Abstract:
- Aerosol particles are a diverse class of materials that permeate the atmosphere with implications for global climate and human health. Atmospheric aerosols are released into the environment from many sources and continue to undergo atmospheric processing which introduces further variation into particle populations. This surfeit of sources and atmospheric trajectories leads to a wide variety in the properties in aerosol particles such as composition, shape, size, morphology, and reactivity. The methods measuring properties of aerosol particles is itself an important and developing field of study with direct applications in bettering our understanding of aerosol behaviors and atmospheric chemical systems. This work presents a critical analysis of existing microscopy-based measurements and provides new methods, applications, and recommendations for improving the assessment of aerosol properties. Chemical properties of aerosol particles include aqueous particle acidity and the O:C ratio of organic constituents. A new method for measuring the internal pH of aqueous aerosol microdroplets was developed and presented here using carbon quantum dots as a pH sensitive fluorophore. This technique was validated using a complex organic mixture representing various functional groups found in atmospheric organic material. The influence of organic O:C ratio on phase separation for proxy organic/inorganic mixed aerosol particles was assessed for microdroplets and nanoparticles. For optical microscope experiments, sucrose was added to organic/inorganic mixtures to systematically increase the O:C ratio of the system and was observed to suppress phase separation. Similarly, particles made up of combinations of carboxylic acids at particular O:C ratios and inorganic salts are analyzed using TEM for size dependence of phase separation at the nanoscale. Generally, large particles are able to phase separate while small particles remain homogeneous, or well mixed, and the transition region between the two regimes was examined. TEM is used in several studies to consider aerosol particle spreading and morphology at atmospherically relevant sizes. Inorganic particles were found to spread along the surface of a substrate. Particles with an organic coating also spread on the substrate but additionally lost volume, possibly due to outgassing of residual volatile species in storage or physical deformation during the impaction process. Results were compared to measurements of the same particles suspended in a gas flow and sizing discrepancies between the two methods were found, mostly attributed to the presence of a substrate in microscope assays. Further, the influence of generation parameters on the final morphologies of particles was determined for particles made under low and high relative humidity conditions with wet and dry seed particles. Wet seeds were found to restructure due to humidity cycling and spread less on the surface than dry seeds, while wet and dry coated particles were influenced similarly by the impaction process. Wet seeded organic particles also showed a new textured morphology, emphasizing the utility of microscope measurements of individual aerosol particles.