Morphology and Optical Properties of Aerosol Particles

Open Access
Author:
Veghte, Daniel Philip
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
January 21, 2015
Committee Members:
  • Miriam Arak Freedman, Dissertation Advisor
  • Lasse Jensen, Committee Member
  • Karl Todd Mueller, Committee Member
  • Jose Dolores Fuentes, Committee Member
Keywords:
  • Aerosol
  • Atmospheric
  • Chemistry
  • Cavity Ring-Down Spectroscopy
  • CRD
  • Electron Microscopy
  • TEM
  • SEM
  • Mineral Dust
  • Organic
Abstract:
Major factors that affect climate change depend on gas and particulate phase components in the atmosphere. Gas phase species have been studied in great detail and are well understood, causing a warming effect on the atmosphere. The less understood major contributing factor in the atmosphere are aerosol particles, which range in size from nanometers up to microns. Aerosol particles can directly scatter and absorb light and also have secondary effects such as acting as a surface for gas phase reactions to occur or seed particles for cloud formation. Aerosol particles can cause health problems ranging from serious cardiovascular to respiratory effects. All Climate and health effects of aerosol particles are dependent on particle composition, morphology, concentration, and size. Since a large variety of particulate types exist in the atmosphere, we have focused on understanding the effect of mineral dust composition and morphology. Mineral dust is important because it is the second largest emission by mass. In order to study the optical properties of aerosol particles, we built a cavity ring-down spectrometer and developed methods to interpret the excinction cross section results for particles with a varied shape. We have studied the major components of mineral dust that include calcium carbonate, hematite, quartz, aluminosilicate clay minerals, and feldspars, along with a heterogeneous dust sample. We have found that non-absorbing species that have surface roughness and an aspect ratio close to one (such as calcite, quartz and feldspar) can be treated as spheres. Aerosol particles that are absorbing (hematite) that have an aspect ratio near one with a roughened surface need to be treated with more complex models; otherwise the extinction cross section will be underrepresented. For aerosol particles that are non-absorbing but have a high aspect ratio (aluminosilicate clay minerals), additional modeling parameters are also needed that will account for shape and orientation. We have used Arizona Test Dust to determine if the models we have developed can be used to model the optical properties of a heterogeneous mixture. We have shown that the extinction cross section of the Arizona Test Dust can be modeled as long as individual components are treated independently and significant error would be introduces if all species were treated as spheres. Organic aerosol particles are chemically complex species that originate from primary or secondary emissions. We have described mixed organic/ammonium sulfate particles in the submicron regime using TEM to understand phase separation. When the organic component has a high aqueous solubility, all particles exhibit a homogeneous morphology while at low aqueous solubility all particles exhibit a phase separated structure. Intermediate solubility organics show a size dependent morphology. For pimelic and succinic acid, small particles (under approximately 200 nm) have a homogeneous structure while the larger particles exhibit phase separated structures. We have studied samples collected in Ulaanbaatar, Mongolia to better understand the types of particles and the effect of aging on these particles in an urban environment. The majority of the particles are soot, small spheres, or mineral dust. When we compared the monthly particle composition, we saw that there was an increased aging of the particles during the winter months due to pollution and a lower boundary layer leading to reduced atmospheric mixing. By understanding the particle composition present in areas and modeling the optical properties of individual particle types, better models can be created to give insight into aerosol particles affects on the atmosphere.