Atmospheric particulate matter pollution during the 2008 Beijing Olympics.

Size fractionated particulate matter (PM) samples (including PM2.5 and PM10) were collected at Peking University in Northwestern Beijing, China for a 2 week period prior to the Olympics, during the 2 week period of the Olympics, and for a 4 week period following the 2008 Olympics, during both source control and nonsource control periods. PM10 concentrations in this study were high correlated with, but a factor of 1.3 times higher than, the Beijing Environmental Protection Bureau's PM10 concentrations at near-by sites because of differences in the measurement methods used. The mean PM2.5 and PM10 concentrations were statistically different, and lower by 31 and 35%, during the Olympic period compared to the non-Olympic period. However, the PM concentrations were not statistically different between the source control and nonsource control periods. While meteorological parameters (air masses from the south and precipitation) accounted for 40% of the total variation in PM10 concentration, source control accounted for 16%, suggesting that meteorology accounted for more of the variation in PM concentration than source control measures. The PM10 concentrations in Beijing during the Olympic period were 2.9, 3.5, and 1.9 times higher than those in Atlanta, Sydney, and Athens. In addition, the PM2.5 and PM10 concentrations during the Olympic period exceeded the WHO 24-h guideline 100% and 81% of the time, respectively. Finally, the PM10 concentrations in October, November, and December 2008 were reduced by 9-27% compared to the same months in 2007, suggesting that the Olympic source control efforts (and possibly a down turn in the economy) have resulted in lower PM10 concentrations in Beijing.

Enantiomeric signatures of organochlorine pesticides in Asian, trans-Pacific, and western U.S. air masses.

The enantiomeric signatures of organochlorine pesticides were measured in air masses from Okinawa, Japan and three remote locations in the Pacific Northwestern United States: Cheeka Peak Observatory (CPO), a marine boundary layer site on the Olympic Peninsula of Washington at 500 m above sea level (m.a.s.l); Mary's Peak Observatory (MPO), a site at 1250 m.a.s.l in Oregon's Coast range; and Mt. Bachelor Observatory (MBO), a site at 2763 m.a.s.l in Oregon's Cascade range. The enantiomeric signatures of composite soil samples, collected from China, South Korea, and the western U.S. were also measured. The data from chiral analysis was expressed asthe enantiomeric fraction, defined as (+) enantiomer/(sum of the (+) and (-) enantiomers), where a racemic composition has EF = 0.5. Racemic alpha-hexachlorocyclohexane (alpha-HCH) was measured in Asian air masses at Okinawa and in Chinese and South Korean soils. Nonracemic alpha-HCH (EF = 0.528 +/- 0.0048) was measured in regional air masses at CPO, and may reflect volatilization from the Pacific Ocean and regional soils. However, during trans-Pacific transport events at CPO, the alpha-HCH EFs were significantly more racemic (EF = 0.513 +/- 0.0003, p < 0.001). Racemic alpha-HCH was consistently measured at MPO and MBO in trans-Pacific air masses that had spent considerable time in the free troposphere. The alpha-HCH EFs in CPO, MPO, and MBO air masses were negatively correlated (p = 0.0017) with the amount of time the air mass spent above the boundary layer, along the 10-day back air mass trajectory, prior to being sampled. This suggests that, on the West coast of the U.S., the alpha-HCH in the free troposphere is racemic. Racemic signatures of cis- and trans-chlordane were measured in air masses at all four air sampling sites, suggesting that Asian and U.S. urban areas continue to be sources of chlordane that has not yet been biotransformed.

Influence of Asian and Western United States urban areas and fires on the atmospheric transport of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and fluorotelomer alcohols in the Western United States.

Atmospheric measurements of semivolatile organic compounds (SOCs) were made at Mt Bachelor Observatory (MBO), located in Oregon's Cascade Range, to understand the trans-Pacific and regional transport of SOCs from urban areas. High volume air sampling (approximately 644 m3 for 24 h periods) of both the gas and particulate phases was conducted from April 19, 2004 to May 13, 2006 (n = 69); including NASA's INTEX-B campaign in spring 2006 (n = 34 of 69). Air mass back trajectories were calculated and were used to calculate source region impact factors (SRIFs), the percentage of time the sampled air mass resided in a given source region. Particulate-phase polycyclic aromatic hydrocarbon (PAH) concentrations at MBO increased with the percentage of air mass time in Asia and, in conjunction with other data, provided strong evidence that particulate-phase PAHs are emitted from Asia and undergo trans-Pacific atmospheric transport to North America. Gas-phase PAH and fluorotelomer alcohol (FTOH) concentrations significantly increased with the percentage of air mass time in California's urban areas, whereas retene and polychlorinated biphenyl (PCB) concentrations increased with the percentage of air mass time in Oregon and during regional fire events. In addition, sigma(gas-phase) PAH, retene, and levoglucosan concentrations were significantly correlated (p-value < 0.001) with sigma(PCB) concentrations, suggesting that increased atmospheric PCB concentrations were associated with fires due to the volatilization of stored PCBs from soil and vegetation.

Influence of Asian and Western United states agricultural areas and fires on the atmospheric transport of pesticides in the Western United States.

Historic and current use pesticides (HUPs and CUPs), with respect to use in the United States and Canada, were identified in trans-Pacific and regional air masses at Mt. Bachelor Observatory (MBO), a remote high elevation mountain in Oregon's Cascade Range located in the United States, during the sampling period of April 2004 to May 2006 (n = 69), including NASA's INTEX-B campaign (spring 2006). Elevated hexachlorobenzene (HCB) and alpha-hexachlorocyclohexane (alpha-HCH) concentrations were measured during trans-Pacific atmospheric transport events at MBO, suggesting that Asia is an important source region for these HUPs. Regional atmospheric transport events at MBO resulted in elevated dacthal, endosulfan, metribuzin, triallate, trifluralin, and chlorpyrifos concentrations, with episodic increases in concentration during some spring application periods, suggesting that the Western U.S. is a significant source region for these CUPs. Endosulfan I, gamma-HCH, and dacthal concentrations were significantly positively correlated (p-value < 0.05) with increased air mass time in Western U.S. agricultural areas. Elevated gamma-HCH concentrations were measured at MBO during both trans-Pacific and regional atmospheric transport events, including regional fire events. In addition to gamma-HCH, elevated sigmachlordane, alpha-HCH, HCB, and trifluralin concentrations were associated with fires in Western North America due to revolatilization of these pesticides from soils and vegetation. Trans-chlordane/cis-chlordane and alpha-HCH/gamma-HCH ratios were calculated and may be used to distinguish between free tropospheric and regional and/or Asian air masses.

Solvent selection for pressurized liquid extraction of polymeric sorbents used in air sampling.

Pressurized liquid extraction (PLE) was evaluated as a method for extracting semivolatile organic compounds (SOCs) from air sampling media, including quartz fiber filter (QFF), polyurethane foam (PUF), and a polystyrene divinyl benzene copolymer (XAD-2). Hansen solubility parameter plots were used to aid in the PLE solvent selection in order to both reduce coextraction of polyurethane and save time in evaluating solvent compatibility during the initial steps of method development. A PLE solvent composition of 75:25% hexane:acetone was chosen for PUF. The XAD-2 copolymer was not solubilized under the PLE conditions used. The average percent PLE recoveries (and percent relative standard deviations) of 63 SOCs, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine, amide, triazine, thiocarbamate, and phosphorothioate pesticides, were 76.7 (6.2), 79.3 (8.1), and 93.4 (2.9)% for the QFF, PUF, and XAD-2, respectively.

Atmospheric outflow of anthropogenic semivolatile organic compounds from East Asia in spring 2004.

To estimate the emissions of anthropogenic semivolatile organic compounds (SOCs) from East Asia and to identify unique SOC molecular markers in Asian air masses, high-volume air samples were collected on the island of Okinawa, Japan between 22 March and 2 May 2004. Contributions from different source regions (China, Japan, the Koreas, Russia, and ocean/local) were estimated by use of source region impact factors (SRIFs). Elevated concentrations of hexachlorobenzene (HCB), hexachlorcyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and particulate-phase polycyclic aromatic hydrocarbons (PAHs) were attributed to air masses from China. A large proportion of the variation in the current-use pesticides, gas-phase PAHs, and polychlorinated biphenyl (PCB) concentrations was explained by meteorology. Chlordanes showed a technical mixture profile and similar concentrations regardless of source region. alpha/gamma HCH and trans/cis chlordane ratios did not vary significantly with different source regions and had regional averages of 2.5 +/- 1.0 and 1.2 +/- 0.3, respectively. Particulate-phase PAH concentrations were significantly correlated (p value < 0.05) with other incomplete combustion byproduct concentrations, including elemental mercury (Hg0), CO, NOx, black carbon, submicrometer aerosols, and SO2. By use of measured PAH, CO, and black carbon concentrations and estimated CO and black carbon emission inventories, the emission of six carcinogenic particulate-phase PAHs was estimated to be 1518-4179 metric tons/year for Asia and 778-1728 metric tons/year for China, respectively. These results confirm that East Asian outflow contains significant emissions of carcinogenic particulate-phase PAHs.

Semivolatile fluorinated organic compounds in Asian and western U.S. air masses.

Semivolatile fluorinated organic compounds (FOCs) were measured in archived air sample extracts collected from Hedo Station Observatory (HSO) on Okinawa, Japan and Mount Bachelor Observatory (MBO), Oregon U.S. during the springs of 2004 (MBO and HSO) and 2006 (MBO). Fluorotelomer alcohols (FTOHs) were measured in both Asian and western U.S. air masses, though western U.S. air masses had significantly higher concentrations. Concentrations of fluorotelomer olefins in Asian air masses and 8:2 fluorotelomer acrylate in U.S. air masses were reported for the first time. N-ethyl perfluorooctane sulfonamide, N-methyl perfluorooctane sulfonamido ethanol, and N-ethyl perfluorooctane sulfonamido ethanol were also measured in Asian and western U.S. air masses but less frequently than FTOHs. The atmospheric sources and fate of FTOHs were investigated by estimating their atmospheric residence times, calculating FTOH concentration ratios, investigating FTOH correlations with nonfluorinated semivolatile organic compound concentrations, and determining air mass back trajectories. Estimated atmospheric residence times for 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH were 50, 80, and 70 d, respectively, and the average concentration ratio of 6:2 FTOH to 8:2 FTOH to 10:2 FTOH at MBO in 2006 was 1.0 to 5.0 to 2.5. The relative order of these atmospheric residence times may explain the observed enhancement of 8:2 FTOH and 10:2 FTOH (relative to 6:2 FTOH) at MBO compared to North American indoor air (FTOH average ratio of 1.0 to 2.0 to 1.0). FTOH concentrations in western U.S. air masses were positively correlated (p < 0.05) with gas-phase polycyclic aromatic hydrocarbon and polychlorinated biphenyl concentrations and negatively correlated (p < 0.05) with agricultural pesticide concentrations. In comparison to western U.S. air masses, trans-Pacific air masses did not contain elevated concentrations of these compounds, whereas lower boundary layer air masses that passed over urban areas of the western U.S. did. This suggests that semivolatile FOCs are emitted from urban areas in the western U.S.

Reduction of 13-deoxydoxorubicin and daunorubicinol anthraquinones by human carbonyl reductase.

Carbonyl reductase (CR) catalyzes the nicotinamide adenine dinucleotide phosphate (NADPH)-dependent reduction of several carbonyls. Anthracyclines used to treat cancer are reduced by CR at the C13 carbonyl and the resulting metabolites are implicated in the cardiotoxicity associated with anthracycline therapy. CR also is believed to have a role in detoxifying quinones, raising the question whether CR catalyzes reduction of anthracycline quinones. Steady-state kinetic studies were done with several anthraquinone-containing compounds, including 13-deoxydoxorubicin and daunorubicinol, which lack the C13 carbonyl, thus unmasking the anthraquinone for study. k(cat) and k(cat)/K(m) values for 13-deoxydoxorubicin and daunorubicinol were nearly identical, indicating that that the efficiency of quinone reduction was unaffected by the differences at the C13 position. k(cat) and k(cat)/K(m) values were much smaller for the analogs than for the parent compounds, suggesting that the C13 carbonyl is preferred as a substrate over the quinone. CR also reduced structurally related quinone molecules with less favorable catalytic efficiency. Modeling studies with doxorubicin and carbonyl reductase revealed that methionine 234 sterically hinder the rings adjacent to the quinone, thus accounting for the lower catalytic efficiency. Reduction of the anthraquinones may further define the role of CR in anthracycline metabolism and may influence anthracycline cytotoxic and cardiotoxic mechanisms.