A Caltech Library Service

Mathematical Modeling of Gas-Phase Organic Air Pollutants


Harley, Robert Adam (1993) Mathematical Modeling of Gas-Phase Organic Air Pollutants. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/va0x-2331.


Volatile organic compounds (VOCs) play a significant role in the production of ozone in urban atmospheres. In addition, VOCs are of concern because some of them are toxic, and because the atmospheric oxidation of directly emitted VOCs can form condensable products which contribute to airborne particulate matter concentrations. In this study, a general model that relates pollutant emissions to ambient VOC concentrations is described. Model performance is evaluated both for ozone and VOCs for the August 27-29, 1987 period in the Los Angeles area using data from the Southern California Air Quality Study (SCAQS). Improved chemical composition profiles for major VOC emission sources are presented, and use of these profiles results in significant changes to previous emissions estimates for many individual VCs. Reconciliation of emission data with speciated ambient VOC concentration data from the Los Angeles area indicates that there is much more unburned gasoline in the atmosphere than the emission inventory suggests. Three photochemical airshed models are presented that predict the ambient concentrations of VOCs. The first model predicts concentrations of lumped VOC classes (e.g. lumped canes, monoalkyl benzenes). Satisfactory model performance is obtained only after the VOC emission estimates prepared by the government are scaled up to match emission rates measured in the Van Nuys tunnel. An enhanced airshed model with 53 individual VOCs represented explicitly also is described and tested. The best performance is obtained for aromatic hydrocarbons which are predicted to within ±20% by the model in most cases; concentrations of most other species are predicted to better than ±50%. Finally, a model for gas-phase toxic organic air pollutants is described and tested for species including aromatics, aldehydes, ketones, and 1,3-butadiene among others. Significant contributions to total ambient concentrations from atmospheric photochemical formation are found for formaldehyde, acetaldehyde, propionaldehyde, acrolein and methyl ethyl ketone. Therefore, control programs for some toxic air pollutants must consider photochemical formation pathways in addition to direct emissions. The novel aspects of this study include the analysis and improvement of speciated VOC emission estimates, and the development and testing of airs hed models for lumped and individual VOCs using data from SCAQS.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:(Environmental Engineering Science)
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Environmental Science and Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Cass, Glen Rowan
Thesis Committee:
  • Cass, Glen Rowan (chair)
  • Brooks, Norman H.
  • Morgan, James J.
  • Seinfeld, John H.
  • Yung, Yuk L.
Defense Date:8 December 1992
Record Number:CaltechETD:etd-08282007-080127
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3256
Deposited By: Imported from ETD-db
Deposited On:31 Aug 2007
Last Modified:29 Jan 2024 22:53

Thesis Files

PDF (Harley_ra_1993.pdf) - Final Version
See Usage Policy.


Repository Staff Only: item control page