Particle size and composition are key factors controlling the impacts of particulate matter (PM) on human health and the environment. A comprehensive method to characterize size-segregated PM organic content was developed, and evaluated during two field campaigns. Size-segregated particles were collected using a cascade impactor (Micro-Orifice Uniform Deposit Impactor) and a PM2.5 large volume sampler. A series of alkanes and polycyclic aromatic hydrocarbons (PAHs) were solvent extracted and quantified using a gas chromatograph coupled with a mass spectrometer (GC/MS). Large volume injections were performed using a programmable temperature vaporization (PTV) inlet to lower detection limits. The developed analysis method was evaluated during the 2001 and 2002 Intercomparison Exercise Program on Organic Contaminants in PM2.5 Air Particulate Matter led by the US National Institute of Standards and Technology (NIST). Ambient samples were collected in May 2002 as part of the Tampa Bay Regional Atmospheric Chemistry Experiment (BRACE) in Florida, USA and in July and August 2004 as part of the New England Air Quality Study - Intercontinental Transport and Chemical Transformation (NEAQS - ITCT) in New Hampshire, USA. Morphology of the collected particles was studied using scanning electron microscopy (SEM). Smaller particles (one micrometer or less) appeared to consist of solid cores surrounded by a liquid layer which is consistent with combustion particles and also possibly with particles formed and/or coated by secondary material like sulfate, nitrate and secondary organic aerosols. Source apportionment studies demonstrated the importance of stationary sources on the organic particulate matter observed at these two rural sites. Coal burning and biomass burning were found to be responsible for a large part of the observed PAHs during the field campaigns. Most of the measured PAHs were concentrated in particles smaller than one micrometer and linked to combustion sources. The presence of known carcinogenic PAHs in the respirable particles has strong importance for human health. Recommendations for method improvements and further studies are included
