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Results are reported from an ongoing passive air monitoring study for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region in Alberta, Canada. Polyurethane foam (PUF) disk passive air samplers were deployed for consecutive 2-month periods from November 2010 to June 2012 at 17 sites. Samples were analyzed for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, dibenzothiophene and its alkylated derivatives (DBTs). Relative to parent PAHs, alkylated PAHs and DBTs are enriched in bitumen and therefore considered to be petrogenic markers. Concentrations in air were in the range 0.03-210 ng/m(3), 0.15-230 ng/m(3) and 0.01-61 ng/m(3) for ∑PAHs, ∑alkylated PAHs and ΣDBTs, respectively. An exponential decline of the PAC concentrations in air with distance from mining areas and related petrogenic sources was observed. The most significant exponential declines were for the alkylated PAHs and DBTs and attributed to their association with mining-related emissions and near-source deposition, due to their lower volatility and greater association with depositing particles. Seasonal trends in concentrations in air for PACs were not observed for any of the compound classes. However, a forest fire episode during April to July 2011 resulted in greatly elevated PAH levels at all passive sampling locations. Alkylated PAHs and DBTs were not elevated during the forest fire period, supporting their association with petrogenic sources. Based on the results of this study, an "Athabasca PAC profile" is proposed as a potential source marker for the oil sands region. The profile is characterized by ∑PAHs/∑Alkylated PAHs = ∼0.2 and ∑PAHs/∑DBTs = ∼5.

The chiral pesticide heptachlor can undergo photolysis to yield the racemic products heptachlor-exo-epoxide (HEPX) and photoheptachlor. Heptachlor is also metabolized to nonracemic HEPX in biological systems and soils. HEPX in ambient air samples from the southern United States and Lakes Ontario and Superior was nonracemic and enriched in the (+) enantiomer. Average enantiomer ratios (ER ) areas of (+)/(-) HEPX) in these locations ranged from 1.51 to 2.02, and were similar to ER values of HEPX reported for agricultural soils. Airborne heptachlor was racemic, with ERs of 0.98-1.02. These results suggest that the main source of HEPX in ambient air is not photolysis of heptachlor, but rather metabolism of heptachlor in soils followed by volatilization of HEPX. The study exemplifies the use of chiral analysis for investigating the environmental fate of pesticides.

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The Global Atmospheric Passive Sampling (GAPS) network, initiated in 2005 across 55 global sites, supports the global monitoring plan (GMP) of the Stockholm Convention on Persistent Organic Pollutants (POPs) by providing information on POP concentrations in air on a global scale. These data inform assessments of the long-range transport potential of POPs and the effectiveness evaluation of chemical regulation efforts, by observing changes in concentrations over time. Currently, measurements spanning 5–10 sampling years are available for 40 sites from the GAPS Network. This study was the first time that POP concentrations in air were reported on a global scale for an extended time period and the first to evaluate worldwide trends with an internally consistent sample set. For consistency between sampling years, site- and sample specific sampling rates were calculated with a new, public online model, which accounts for the effects of wind speed variability. Concentrations for legacy POPs in air between 2005 and 2014 show different trends for different organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The POPs discussed in this study were chosen due to being the most frequently detected, with detection at the majority of sites. PCB, endosulfan, and hexachlorocyclohexane (HCH) concentrations in air are decreasing at most sites. The global trends reflect global sources and recycling of HCH, ongoing emissions from old stockpiles for PCBs, and recent use restrictions for endosulfan. These chlorinated OCPs continue to present exposure threat to humans and ecosystems worldwide. Concentrations of other OCPs, such as chlordanes, heptachlor and dieldrin, are steady and/or declining slowly at the majority of sites, reflecting a transition from primary to secondary sources (i.e., re-emission from reservoirs where these POPs have accumulated historically) which now control ambient air burdens.

Long-term air monitoring data for POPs are required to determine the effectiveness of source reduction measures and factors controlling air concentrations. Air samples were collected between 1992 and 2012 at three sites with different geographical characteristics (Burnt Island, Egbert and Point Petre) in the Canadian Great Lakes Basin (GLB) using high-volume samplers and analyzed for organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Spatial and temporal trends of gas-phase concentrations of OCPs, selected PCB congeners and ƩPCBs (84 congeners) were assessed. Egbert had the highest concentrations of some OCPs due to historical [dichlorodiphenyltrichloroethanes (DDTs), dieldrin, γ-hexachlorocyclohexane (γ-HCH)] and current (endosulfan) applications of these pesticides in the surrounding agricultural cropland. This shows that agricultural areas are a source of OCPs to the GLB. High o,p'-/p,p'-DDT ratios were determined and an increasing trend was observed at Point Petre and Burnt Island up to 2004; indicating that the GLB is influenced by dicofol-type DDT sources, which have higher o,p'-/p,p'-DDT ratios than technical DDT. Atmospheric PCB concentrations at Egbert and Point Petre are higher than those measured at Burnt Island, likely due to urban influence and greater populations. Loadings calculations suggest that the atmosphere is a source of α-endosulfan and p,p'-DDT to the lakes and the opposite is true for p,p'-DDE. Long-term decreasing trends were observed for both OCPs and PCBs; consistent with control measures implemented in North America. Atmospheric PCB concentrations are decreasing relatively slowly, with halflives in the range of 9-39 years. Chlordane, α-endosulfan, β-endosulfan, dieldrin, and DDT-related substances showed halflives in the range of 7-13 years. α-HCH and γ-HCH were decreasing rapidly in air, with halflives of 5 years. Long-term declining trends of PCBs and OCPs suggest that regulatory efforts to reduce emissions to the GLB environment have been effective, but emissions from primary and secondary sources might limit future declines.

Extracts of passive air samples collected from 15 passive sampling network sites across the Athabasca Oil Sands region were used to explore the application of in vitro assays for mutagenicity (Salmonella mutation assays) and cytotoxicity (lactate dehydrogenase assay) to assess the toxicity of the air mixture. The air monitoring of polycyclic aromatic compounds (PACs) and PAC transformation products, including nitrated polycyclic aromatic hydrocarbons (NPAHs) and oxygenated polycyclic aromatic hydrocarbons (OPAHs) was then linked to the potential toxicity of air. The PACs in air during April to May 2014 were elevated near mining activities and declined with distance from the source region, whereas NPAHs and OPAHs exhibited a more variable spatial distribution with the highest levels in Fort McMurray. Overall, the air samples exhibited a weak mutagenicity. The highest indirect-acting mutagenicity was observed for sites closest to mining activities; however, the indirect-acting mutagenicity did not decline sharply with distance from mining areas. Indirect-acting mutagenicity was strongly correlated with levels of total PACs, benzo(a)pyrene equivalent mass, and OPAHs. Most of the samples exhibited cytotoxic potential, but the magnitude of the response was variable across the sample region and did not correlate with levels of target analytes. This indicates that PACs and PAC derivatives were not a major contributor to the cytotoxicity observed in the air samples.

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