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Polycyclic aromatic hydrocarbons (PAHs) have toxic impacts on humans and ecosystems. One of the most carcinogenic PAHs, benzo(a)pyrene (BaP), is efficiently bound to and transported with atmospheric particles. Laboratory measurements show that particle-bound BaP degrades in a few hours by heterogeneous reaction with ozone, yet field observations indicate BaP persists much longer in the atmosphere, and some previous chemical transport modeling studies have ignored heterogeneous oxidation of BaP to bring model predictions into better agreement with field observations. We attribute this unexplained discrepancy to the shielding of BaP from oxidation by coatings of viscous organic aerosol (OA). Accounting for this OA viscosity-dependent shielding, which varies with temperature and humidity, in a global climate/chemistry model brings model predictions into much better agreement with BaP measurements, and demonstrates stronger long-range transport, greater deposition fluxes, and substantially elevated lung cancer risk from PAHs. Model results indicate that the OA coating is more effective in shielding BaP in the middle/high latitudes compared with the tropics because of differences in OA properties (semisolid when cool/dry vs. liquid-like when warm/humid). Faster chemical degradation of BaP in the tropics leads to higher concentrations of BaP oxidation products over the tropics compared with higher latitudes. This study has profound implications demonstrating that OA strongly modulates the atmospheric persistence of PAHs and their cancer risks., Competing Interests: The authors declare no conflict of interest.

Contaminants used at low elevation, such as pesticides on crops, can be transported tens of kilometers and deposited in adjacent mountains in many parts of the world. Atmospherically deposited organic contaminants in the Sierra Nevada Mountains of California, USA, have exceeded some thresholds of concern, but the spatial and temporal distributions of contaminants in the mountains are not well known. The authors sampled shallow-water sediment and tadpoles (Pseudacris sierra) for pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls in four high-elevation sites in Yosemite National Park in the central Sierra Nevada twice during the summers of 2006, 2007, and 2008. Both historic- and current-use pesticides showed a striking pattern of lower concentrations in both sediment and tadpoles in Yosemite than was observed previously in Sequoia-Kings Canyon National Parks in the southern Sierra Nevada. By contrast, PAH concentrations in sediment were generally greater in Yosemite than in Sequoia-Kings Canyon. The authors suggest that pesticide concentrations tend to be greater in Sequoia-Kings Canyon because of a longer air flow path over agricultural lands for this park along with greater pesticide use near this park. Concentrations for DDT-related compounds in some sediment samples exceeded guidelines or critical thresholds in both parks. A general pattern of difference between Yosemite and Sequoia-Kings Canyon was not evident for total tadpole cholinesterase activity, an indicator of harmful exposure to organophosphorus and carbamate pesticides. Variability of chemical concentrations among sites, between sampling periods within each year, and among years, contributed significantly to total variation, although the relative contributions differed between sediment and tadpoles., (Copyright © 2013 SETAC.)