Staci L. Massey Simonich

Concentration and photochemistry of PAHs, NPAHs, and OPAHs and toxicity of PM2.5 during the Beijing Olympic Games.

Atmospheric particulate matter with diameter <2.5 um (PM(2.5)) 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 PM(2.5) 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 periods. However, the mutagenicity of the PM(2.5) was significantly reduced only during the Olympic period. The PAH, NPAH, and OPAH composition of the PM(2.5) 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 SO(2) 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 ∑NPAH and ∑OPAH 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 PM(2.5) in Beijing.

Concentrations, sources and spatial distribution of polycyclic aromatic hydrocarbons in soils from Beijing, Tianjin and surrounding areas, North China

The concentrations, profiles, sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) were determined in 40 surface soil samples collected from Beijing, Tianjin and surrounding areas, North China in 2007, and all sampling sites were far from industrial areas, roadsides and other pollution sources, and across a range of soil types in remote, rural villages and urban areas. The total concentrations of 16 PAHs ranged from 31.6 to 1475.0 ng/g, with an arithmetic average of 336.4 ng/g. The highest PAH concentrations were measured in urban soils, followed by rural village soils and soils from remote locations. The remote-rural village-urban PAH concentration gradient was related to population density, gross domestic product (GDP), long-range atmospheric transport and different types of land use. In addition, the PAH concentration was well correlated with the total organic carbon (TOC) concentration of the soil. The PAH profile suggested that coal combustion and biomass burning were primary PAH sources.

Occurrence and exposure to polycyclic aromatic hydrocarbons and their derivatives in a rural Chinese home through biomass fuelled cooking.

The concentration and composition of PAHs emitted from biomass cooking fuel were characterized in a rural non-smoking household in northern China. Twenty-two parent PAHs (pPAHs), 12 nitro-PAHs (nPAHs), and 4 oxy-PAHs (oPAHs) were measured in the kitchen, bedroom, and outdoors during both summer and winter. The most severe contamination occurred in the kitchen in the winter, where the daily mean concentrations of pPAHs, nPAHs, and oPAHs were 7500 ± 4100, 38 ± 29, and 8400 ± 9200 ng/m(3), respectively. Our results suggest that the nPAHs were largely from secondary formation in ambient air while oPAHs were either from primary emission of biomass burning or secondary formation from pPAHs in the kitchen. The daily mean benzo(a)pyrene equivalent exposure concentration was as high as 200 ± 160 ng/m(3) in the winter for the housewife who did the cooking compared to 59 ± 37 ng/m(3) for the control group that did not cook.

Estimated reduction in cancer risk due to PAH exposures if source control measures during the 2008 Beijing Olympics were sustained.

Background The 2008 Beijing Olympic Games provided a unique case study to investigate the effect of source control measures on the reduction in air pollution, and associated inhalation cancer risk, in a Chinese megacity. Objectives We measured 17 carcinogenic polycyclic aromatic hydrocarbons (PAHs) and estimated the lifetime excess inhalation cancer risk during different periods of the Beijing Olympic Games, to assess the effectiveness of source control measures in reducing PAH-induced inhalation cancer risks. Methods PAH concentrations were measured in samples of particulate matter ≤ 2.5 μm in aerodynamic diameter (PM2.5) collected during the Beijing Olympic Games, and the associated inhalation cancer risks were estimated using a point-estimate approach based on relative potency factors. Results We estimated the number of lifetime excess cancer cases due to exposure to the 17 carcinogenic PAHs [12 priority pollutant PAHs and five high-molecular-weight (302 Da) PAHs (MW 302 PAHs)] to range from 6.5 to 518 per million people for the source control period concentrations and from 12.2 to 964 per million people for the nonsource control period concentrations. This would correspond to a 46% reduction in estimated inhalation cancer risk due to source control measures, if these measures were sustained over time. Benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[a]pyrene, and dibenzo[a,l]pyrene were the most carcinogenic PAH species evaluated. Total excess inhalation cancer risk would be underestimated by 23% if we did not include the five MW 302 PAHs in the risk calculation. Conclusions Source control measures, such as those imposed during the 2008 Beijing Olympics, can significantly reduce the inhalation cancer risk associated with PAH exposure in Chinese megacities similar to Beijing. MW 302 PAHs are a significant contributor to the estimated overall inhalation cancer risk.

Emissions of Parent, Nitro, and Oxygenated Polycyclic Aromatic Hydrocarbons from Residential Wood Combustion in Rural China

Residential wood combustion is one of the important sources of air pollution in developing countries. Among the pollutants emitted, parent polycyclic aromatic hydrocarbons (pPAHs) and their derivatives, including nitrated and oxygenated PAHs (nPAHs and oPAHs), are of concern because of their mutagenic and carcinogenic effects. In order to evaluate their impacts on regional air quality and human health, emission inventories, based on realistic emission factors (EFs), are needed. In this study, the EFs of 28 pPAHs (EF(PAH28)), 9 nPAHs (EF(PAHn9)), and 4 oPAHs (EF(PAHo4)) were measured for residential combustion of 27 wood fuels in rural China. The measured EF(PAH28), EF(PAHn9), and EF(PAHo4) for brushwood were 86.7 ± 67.6, 3.22 ± 1.95 × 10(-2), and 5.56 ± 4.32 mg/kg, which were significantly higher than 12.7 ± 7.0, 8.27 ± 5.51 × 10(-3), and 1.19 ± 1.87 mg/kg for fuel wood combustion (p < 0.05). Sixteen U.S. EPA priority pPAHs contributed approximately 95% of the total of the 28 pPAHs measured. EFs of pPAHs, nPAHs, and oPAHs were positively correlated with one another. Measured EFs varied obviously depending on fuel properties and combustion conditions. The EFs of pPAHs, nPAHs, and oPAHs were significantly correlated with modified combustion efficiency and fuel moisture. Nitro-naphthalene and 9-fluorenone were the most abundant nPAHs and oPAHs identified. Both nPAHs and oPAHs showed relatively high tendencies to be present in the particulate phase than pPAHs due to their lower vapor pressures. The gas-particle partitioning of freshly emitted pPAHs, nPAHs, and oPAHs was primarily controlled by organic carbon absorption.

Atmospheric concentrations and air–soil gas exchange of polycyclic aromatic hydrocarbons (PAHs) in remote, rural village and urban areas of Beijing–Tianjin region, North China

Forty passive air samplers were deployed to study the occurrence of gas and particulate phase PAHs in remote, rural village and urban areas of Beijing-Tianjin region, North China for four seasons (spring, summer, fall and winter) from 2007 to 2008. The influence of emissions on the spatial distribution pattern of air PAH concentrations was addressed. In addition, the air-soil gas exchange of PAHs was studied using fugacity calculations. The median gaseous and particulate phase PAH concentrations were 222 ng/m³ and 114 ng/m³, respectively, with a median total PAH concentration of 349 ng/m³. Higher PAH concentrations were measured in winter than in other seasons. Air PAH concentrations measured at the rural villages and urban sites in the northern mountain region were significantly lower than those measured at sites in the southern plain during all seasons. However, there was no significant difference in PAH concentrations between the rural villages and urban sites in the northern and southern areas. This urban-rural PAH distribution pattern was related to the location of PAH emission sources and the population distribution. The location of PAH emission sources explained 56%-77% of the spatial variation in ambient air PAH concentrations. The annual median air-soil gas exchange flux of PAHs was 42.2 ng/m²/day from soil to air. Among the 15 PAHs measured, acenaphthylene (ACY) and acenaphthene (ACE) contributed to more than half of the total exchange flux. Furthermore, the air-soil gas exchange fluxes of PAHs at the urban sites were higher than those at the remote and rural sites. In summer, more gaseous PAHs volatilized from soil to air because of higher temperatures and increased rainfall. However, in winter, more gaseous PAHs deposited from air to soil due to higher PAH emissions and lower temperatures. The soil TOC concentration had no significant influence on the air-soil gas exchange of PAHs.

Polystyrene plastic: a source and sink for polycyclic aromatic hydrocarbons in the marine environment

Polycyclic aromatic hydrocarbons (PAHs) on virgin polystyrene (PS) and PS marine debris led us to examine PS as a source and sink for PAHs in the marine environment. At two locations in San Diego Bay, we measured sorption of PAHs to PS pellets, sampling at 0, 1, 3, 6, 9, and 12 months. We detected 25 PAHs using a new analytical method with comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. Several congeners were detected on samples before deployment. After deployment, some concentrations decreased (1,3-dimethylnaphthalene and 2,6-methylnaphthalene), while most increased [2-methylanthracene and all parent PAHs (PPAHs), except fluorene and fluoranthene], suggesting that PS debris is a source and sink for PAHs. When sorbed concentrations of PPAHs on PS are compared to the five most common polymers [polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), and polypropylene (PP)], PS sorbed greater concentrations than PP, PET, and PVC, similar to HDPE and LDPE. Most strikingly, at 0 months, PPAHs on PS ranged from 8 to 200 times greater than on PET, HDPE, PVC, LDPE, and PP. The combination of greater PAHs in virgin pellets and large sorption suggests that PS may pose a greater risk of exposure to PAHs upon ingestion.

Inhalation Cancer Risk Associated with Exposure to Complex Polycyclic Aromatic Hydrocarbon Mixtures in an Electronic Waste and Urban Area in South China

Atmospheric particulate matter samples were collected from May 2010 to April 2011 in a rural e-waste area and in Guangzhou, South China, to estimate the lifetime inhalation cancer risk from exposure to parent polycyclic aromatic hydrocarbons (PAHs), high molecular weight PAHs (MW 302 PAHs), and halogenated PAHs (HPAHs). Seasonal variations in the PAH concentrations and profiles within and between the e-waste and urban areas indicated different PAH sources in the two areas. Benzo[b]fluoranthene, benzo[a]pyrene, dibenz[ah]anthracene, and dibenzo[al]pyrene made the most significant contribution to the inhalation cancer risk. MW 302 PAHs accounted for 18.0% of the total cancer risk in the e-waste area and 13.6% in the urban area, while HPAHs made a minor contribution (<0.1%) in both the areas. The number of lifetime excess lung cancers due to exposure to parent PAHs, MW 302 PAHs, and HPAHs ranged from 15.1 to 1198 per million people in the e-waste area and from 9.3 to 737 per million people in Guangzhou. PAH exposure accounted for 0.02 to 1.94% of the total lung cancer cases in Guangzhou. On average, the inhalation cancer risk in the e-waste area was 1.6 times higher than in the urban area. The e-waste dismantling activities in South China led to higher inhalation cancer risk due to PAH exposure than the urban area.

Endosulfan I and endosulfan sulfate disrupts zebrafish embryonic development

Fish in agricultural and remote areas may be exposed to endosulfan and its degradation products as a result of direct runoff, atmospheric transport and deposition. The following study used the zebrafish developmental model to investigate the responses to endosulfan I and endosulfan sulfate, the major degradation product of endosulfan I and II. Embryos were dechorionated and waterborne exposed to the endosulfan I or endosulfan sulfate from 6 to 120h post-fertilization (hpf). Endosulfan I exposure concentrations ranged from 0.01 to 10microg/L and endosulfan sulfate from 1 to 100microg/L. Water solutions were renewed every 24h and fish were scored for overt developmental and behavioral abnormalities. Chemical analysis was performed on water, whole embryo, and larvae samples to determine waterborne exposure concentrations and tissue concentrations throughout the 5-day period. The most sensitive toxicity endpoint for both endosulfan I and endosulfan sulfate was an abnormal response of the embryo/larvae to touch, suggesting that endosulfan I and sulfate are developmentally neurotoxic. The waterborne exposure EC(50)s for inhibition of touch response for endosulfan I and endosulfan sulfate were 2.2microg/L and 23microg/L, respectively. The endosulfans were highly concentrated by the organisms, and the inhibition of touch response tissue EC(50), determined from the measured tissue concentrations, was 367ng/g for endosulfan I and 4552ng/g for endosulfan sulfate.

Sources and Deposition of Polycyclic Aromatic Hydrocarbons to Western U.S. National Parks

Seasonal snowpack, lichens, and lake sediment cores were collected from fourteen lake catchments in eight western U.S. National Parks and analyzed for sixteen polycyclic aromatic hydrocarbons (PAHs) to determine their current and historical deposition, as well as to identify their potential sources. Seasonal snowpack was measured to determine the current wintertime atmospheric PAH deposition; lichens were measured to determine the long-term, year around deposition; and the temporal PAH deposition trends were reconstructed using lake sediment cores dated using (210)Pb and (137)Cs. The fourteen remote lake catchments ranged from low-latitude catchments (36.6 degrees N) at high elevation (2900 masl) in Sequoia National Park, CA to high-latitude catchments (68.4 degrees N) at low elevation (427 masl) in the Alaskan Arctic. Over 75% of the catchments demonstrated statistically significant temporal trends in SigmaPAH sediment flux, depending on catchment proximity to source regions and topographic barriers. The SigmaPAH concentrations and fluxes in seasonal snowpack, lichens, and surficial sediment were 3.6 to 60,000 times greater in the Snyder Lake catchment of Glacier National Park than the other 13 lake catchments. The PAH ratios measured in snow, lichen, and sediment were used to identify a local aluminum smelter as a major source of PAHs to the Snyder Lake catchment. These results suggest that topographic barriers influence the atmospheric transport and deposition of PAHs in high-elevation ecosystems and that PAH sources to these national park ecosystems range from local point sources to diffuse regional and global sources.