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Secondary Organic Aerosol Composition Studies Using Mass Spectrometry

Citation

Schilling, Katherine Ann (2015) Secondary Organic Aerosol Composition Studies Using Mass Spectrometry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z93F4MJR. http://resolver.caltech.edu/CaltechTHESIS:05222015-145550415

Abstract

Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NOx and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH4)2SO4 seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:atmospheric aerosol, mass spectrometry, alkanes, toluene, cresol
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:Department of Defense Science, Mathematics, and Research for Transformation Fellowship
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Seinfeld, John H.
Thesis Committee:
  • Beauchamp, Jesse L. (chair)
  • Blake, Geoffrey A.
  • Okumura, Mitchio
  • Seinfeld, John H.
Defense Date:18 May 2015
Non-Caltech Author Email:kaschilling (AT) gmail.com
Funders:
Funding AgencyGrant Number
U.S. Department of EnergyDE-SC 0006626
National Science FoundationAGS-1057183
Record Number:CaltechTHESIS:05222015-145550415
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:05222015-145550415
DOI:10.7907/Z93F4MJR
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8881
Collection:CaltechTHESIS
Deposited By: Katherine Schilling
Deposited On:02 Jun 2015 15:30
Last Modified:12 Apr 2016 21:01

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