Intraurban concentrations, spatial variability and correlation of ambient aromatic hydrocarbons (PAH) and PM2.5

To investigate the intraurban spatial variability of air toxics associated with respirable particulate matter (PM), ambient PM2.5 and 16 polycyclic aromatic hydrocarbons (PAH) species (vapour phase plus 2.5 mm particle phase) were sampled over a dense network of sites in Hamilton, Ontario, Canada in June/July 2009 and December 2009. PM2.5 levels ranged from 2.46 to 11.0 ug m^-3 in the summer campaign and 6.52 to 13.4 ug m^-3 in the winter campaign. Total sampled PAH (S16PAH) levels ranged from 10.2 to 83.7 ng m^-3 in the summer campaign and 8.31 to 52.1 ng m^-3 in the winter campaign. Ambient PM2.5 and PAH concentrations were greater below the city's escarpment with a below/above escarpment difference in concentration much greater for PAH than for PM2.5 in both summer and winter sampling campaigns. Elevated levels of both pollutants were observed to occur near or downwind of the central business district and industrialized harbourfront area, suggesting the contribution of local sources. Ambient PAH exhibited a substantially greater degree of intraurban variability than PM2.5 (coefficient of variation approximately three times greater in summer campaign, four times greater in winter campaign) both above and below the escarpment, particularly for heavy MW species found predominantly in the particle phase. Benzo(a)Pyrene-equivalent toxicity (BaP-TEQ) associated with ambient PAH showed a generally similar spatial distribution to S16PAH; however, several sites with relatively low S16PAH had high BaP-TEQ (enriched in more toxic heavy MW species), indicating potential hotspots for elevated PAH exposures and local source contributions. Co-located field sampling data showed that central site monitoring was a poor proxy for PM2.5 and particularly for PAH and associated toxicity (BaP-TEQ) across the urban centre, underestimating levels at many sites, likely due to the significant number of locally distributed sources and mixed land use. The much greater intraurban variability of PAH relative to PM2.5, particularly for toxic heavy MW species predominantly in particle phase, demonstrated variability in PM2.5 composition and confirmed the importance of the local scale for PAH exposure health risk assessment.