Characterization of Polycyclic Aromatic Hydrocarbons (PAH) in airborne particles and assessment of human exposure to PAHs

Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic air pollutants formed during incomplete combustion and are ubiquitously distributed in the environment. To determine particle-bound PAHs in archived PM2.5 samples taken with low flow rate in Atlanta, a sensitive and robust method was developed for measuring 28 PAHs and methyl PAHs in PM samples using isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS). The method was then used to analyze PM2.5 samples collected at three sites (rural, urban, suburban-highway) from the Assessment of Spatial Aerosol Composition in Atlanta (ASACA) network. Distinct seasonal and spatial variations were observed in PAH concentration. Particle-bound PAH levels were significantly higher in winter than in summer. The suburban-highway site had higher PM2.5-bound PAH concentration than did the urban site, and the rural site had the lowest PAH levels. Retene, a proposed biomass burning tracer, captured both the high leaves-grasses-bushes-branches burning season and the high wood burning months, suggesting that it might be a better marker for all biomass burning, while potassium ion might be a more specific tracer for wood burning. Human exposure to PAHs can be assessed by characterizing their hydroxy PAH (OH-PAH) metabolites in urine samples. A method was developed to measure 24 urinary OH-PAHs, metabolites of 8 parent PAHs, using enzymatic de-conjugation, automatic liquid-liquid extraction, and GC/HRMS. A study was then carried out to evaluating the variability of the urinary biomarker levels in a non-occupationally exposed non-smoking reference group. Levels of urinary PAH metabolites varied widely both within-subject and between-subjects and the within-day variance far exceeded the between-day variance. There were also considerable temporal correlations for these biomarkers. Sample size calculations were conducted and taking 24-hour voids would require the least number of subjects, which should be considered during epidemiological study design. Finally, a study was conducted to evaluate exposure to ambient PAHs in an urban setting among 8 non-occupationally exposed non-smoking volunteers employing both personal air sampling and urine biomonitoring. PAH levels varied largely in air samples taken at home, at work, and while driving or jogging. Monitoring urinary OH-PAH levels can capture both inhalation and dietary exposures. Total inhaled PAH was correlated with total excreted OH-PAHs, suggesting that by combining personal air sampling and biomonitoring, exposure to environmental PAHs can be well characterized even for low-level exposure.Ph.D.Committee Chair: Mulholland, James A.; Committee Member: Bergin, Michael H.; Committee Member: Patterson Jr., Donald G.; Committee Member: Russell, Armistead G.; Committee Member: Sjodin, Andreas; Committee Member: Wine, Paul H