PM(2.5) Characterization for Time Series Studies: Organic Molecular Marker Speciation Methods and Observations from Daily Measurements in Denver.

Particulate matter less than 2.5 microns in diameter (PM(2.5)) has been shown to have a wide range of adverse health effects and consequently is regulated in accordance with the US-EPA's National Ambient Air Quality Standards. PM(2.5) originates from multiple primary sources and is also formed through secondary processes in the atmosphere. It is plausible that some sources form PM(2.5) that is more toxic than PM(2.5) from other sources. Identifying the responsible sources could provide insight into the biological mechanisms causing the observed health effects and provide a more efficient approach to regulation. This is the goal of the Denver Aerosol Sources and Health (DASH) study, a multi-year PM(2.5) source apportionment and health study.The first step in apportioning the PM(2.5) to different sources is to determine the chemical make-up of the PM(2.5). This paper presents the methodology used during the DASH study for organic speciation of PM(2.5). Specifically, methods are covered for solvent extraction of non-polar and semi-polar organic molecular markers using gas chromatography-mass spectrometry (GC-MS). Vast reductions in detection limits were obtained through the use of a programmable temperature vaporization (PTV) inlet along with other method improvements. Results are presented for the first 1.5 years of the DASH study revealing seasonal and source-related patterns in the molecular markers and their long-term correlation structure. Preliminary analysis suggests that point sources are not a significant contributor to the organic molecular markers measured at our receptor site. Several motor vehicle emission markers help identify a gasoline/diesel split in the ambient data. Findings show both similarities and differences when compared with other cities where similar measurements and assessments have been made.