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Constraining Anthropogenic and Biogenic Emissions using Chemical Ionization Mass Spectrometry


Spencer, Kathleen Marie (2011) Constraining Anthropogenic and Biogenic Emissions using Chemical Ionization Mass Spectrometry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/XRFJ-2Q92.


Numerous gas-phase anthropogenic and biogenic compounds are emitted into the atmosphere. These gases undergo oxidation to form other gas-phase species and particulate matter. Whether directly or indirectly, primary pollutants, secondary gas-phase products, and particulate matter all pose health and environmental risks. In this work, ambient measurements conducted using chemical ionization mass spectrometry are used as a tool for investigating regional air quality.

Ambient measurements of peroxynitric acid (HO₂NO₂) were conducted in Mexico City. A method of inferring the rate of ozone production, PO3, is developed based on observations of HO₂NO₂, NO, and NO₂. Comparison of this observationally based PO3 to a highly constrained photochemical box model indicates that regulations aimed at reducing ozone levels in Mexico City by reducing NOx concentrations may be effective at higher NOx levels than predicted using accepted photochemistry.

Measurements of SO₂ and particulate sulfate were conducted over the Los Angeles basin in 2008 and are compared to measurements made in 2002. A large decrease in SO₂ concentration and a change in spatial distribution are observed. Nevertheless, only a modest reduction in sulfate concentration is observed at ground sites within the basin. Possible explanations for these trends are investigated.

Two techniques, single and triple quadrupole chemical ionization mass spectrometry, were used to quantify ambient concentrations of biogenic oxidation products, hydroxyacetone and glycolaldehyde. The use of these techniques demonstrates the advantage of triple quadrupole mass spectrometry for separation of mass analogues, provided the collision-induced daughter ions are sufficiently distinct. Enhancement ratios of hydroxyacetone and glycolaldehyde in Californian biomass burning plumes are presented as are concentrations of these compounds at a rural ground site downwind of Sacramento.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:chemical ionization mass spectrometry; peroxynitric acid; sulfur dioxide; hydroxyacetone; glycolaldehyde; Los Angeles Basin
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Wennberg, Paul O. (advisor)
  • Okumura, Mitchio (co-advisor)
Thesis Committee:
  • Beauchamp, Jesse L. (chair)
  • Wennberg, Paul O.
  • Okumura, Mitchio
  • Blake, Geoffrey A.
  • Seinfeld, John H.
Defense Date:31 May 2011
Record Number:CaltechTHESIS:05262011-132849976
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6452
Deposited By: Kathleen Spencer
Deposited On:13 Sep 2012 18:29
Last Modified:09 Oct 2019 17:10

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