Detailed molecular and isotopic characterization of carbonaceous aerosols to assess air quality issues in urban areas : the San Francisco Bay Area and the Houston metropolitan area.

The objective of this dissertation is to provide detailed characterization of carbonaceous organic aerosols to better understand major sources of particulate matter (PM) and their atmospheric formation in an oxidizing and highly complex urban atmosphere. For this dissertation, optimized radiocarbon (14C) and source characterization techniques were applied to PM samples from the Houston Metropolitan Area and the San Francisco Bay Area. The San Francisco Bay area study was focused on identifying seasonal trends (winter and non-winter) and sources of elemental carbon (EC). The study required isolation of EC for 14C-based source apportionment. Chemical mass balance model (CMB) of EC and 14C-based total organic carbon (TOC; OC + EC) were also included for comparison of source apportionment methods and different carbonaceous aerosol fractions, respectively. Sources of EC and TOC were similar at most of the sites while a few sites (e.g. San Francisco and Napa) were distinctively more impacted by fossil fuel or contemporary/biomass burning sources. The winter season had significantly larger TOC concentration due to meteorological conditions and changes in emissions (e.g. increased residential wood smoke). Relatively good agreement between the 14C-EC- and CMB-EC- was observed for both seasons. The first and second Houston studies focused on identifying diurnal and temporal trends of aerosols using both fine and coarse PM and contribution of secondary organic carbon during periods of poor air quality (i.e. high ozone and PM), respectively. The largest concentrations of fine EC and BC concentrations occured during the mornings while periods of enhanced TOC was driven by an increase in the fine PM. Interestingly, a relatively large contribution of coarse EC was measured in Houston. Based on the 14C and CMB analysis, Houston’s carbonaceous aerosols are largely from secondary biogenic sources while secondary fossil contribution was highly variable. Furthermore, the poor air quality period in the Houston metropolitan area was driven by favorable meteorological conditions (i.e. Bay Breeze) providing stagnant atmospheric conditions, allowing for accumulation and photooxidation of fossil fuel emissions. Overall, the study results provided up-to-date characterization and source apportionment of less studied carbonaceous aerosols fractions at two major U.S. urban coastal regions.