The global distribution of 22 potentially harmful organochlorine compounds was investigated in more than 200 tree bark samples from 90 sites worldwide. High concentrations of organochlorines were found not only in some developing countries but also in industrialized countries, which continue to be highly contaminated even though the use of many of these compounds is restricted. The distribution of relatively volatile organochlorine compounds (such as hexachlorobenzene) is dependent on latitude and demonstrates the global distillation effect, whereas less volatile organochlorine compounds (such as endosulfan) are not as effectively distilled and tend to remain in the region of use.
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.
Atmospheric particulate matter with diameter <2.5 um (PM2.5) was collected at Peking University (PKU) in Beijing, China before, during, and after the 2008 Olympics and analyzed for black carbon (BC), organic carbon (OC), lower molecular weight (MW<300) and MW302 Polycyclic Aromatic Hydrocarbons (PAHs), nitrated PAHs (NPAHs) and oxygenated PAHs (OPAHs). In addition, the direct and indirect acting mutagenicity of the PM2.5 and the potential for DNA damage to human lung cells were also measured. Significant reductions in BC (45%), OC (31%), MW< 300 PAH (26% – 73%), MW 302 PAH (22% – 77%), NPAH (15% – 68%) and OPAH (25% – 53%) concentrations were measured during the source control and Olympic Olympic period. However, the mutagenicity of the PM2.5 was significantly reduced only during the Olympic period. The PAH, NPAH, and OPAH composition of the PM2.5 was similar throughout the study, suggesting similar sources during the different periods. During the source control period, the parent PAH concentrations were correlated with NO, CO, and SO2 concentrations, indicating that these PAHs were associated with both local and regional emissions. However, the NPAH and OPAH concentrations were only correlated with the NO concentrations, indicating that the NPAH and OPAH were primarily associated with local emissions. The relatively high 2-nitrofluoranthene/1-nitropyrene ratio (25 – 46) and 2-nitrofluoranthene/2-nitropyrene ratio (3.4 – 4.8), suggested a predominance of photochemical formation of NPAHs through OH-radical-initiated reactions in the atmosphere. On average, the ΣNPAH and ΣOPAH concentrations were 8% of the parent PAH concentrations, while the direct-acting mutagenicity (due to the NPAH and OPAH) was 200% higher than the indirect-acting mutagenicity (due to the PAH). This suggests that NPAH and OPAH make up a significant portion of the overall mutagenicity of PM2.5 in Beijing.
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