Occurrence and carcinogenic potential of airborne polycyclic aromatic hydrocarbons in some large-scale enclosed/semi-enclosed vehicle parking areas.

Polycyclic aromatic hydrocarbons (PAHs) originating from vehicle exhaust have aroused much attention due to their potential healthy effect. In this study, air samples were collected from three representative parking lots in a metropolitan area, analyzed for PAHs and evaluated for inhalation risk. Atmospheric PAH levels of these parking areas ranged between 1,178-4,793 ng m(-3), one order of magnitude higher than general urban areas. Their benzo[a]pyrene equivalent (BaPeq) values varied in 11.0-98.0 ng m(-3), far exceeding the air quality standard of WHO (1.0 ng m(-3)). Monte Carlo simulation (100,000 trials) results suggest that the potential lifetime inhalation cancer risks of PAHs were 0.27 × 10(-5) to 7.11 × 10(-5) for park employees, which are in the acceptable range acknowledged by US EPA (1.0 × 10(-6) to 1.0 × 10(-4)). Several source diagnostic methods proved that vehicle exhaust was the dominant PAH contributor of these parks with the contribution percentages being >53%; oil combustion and/or coal combustion were other important sources. Logarithms of gas-particle distribution coefficients (Kps) of PAHs in all studied parks were linearly correlated with those of both their sub-cooled vapor pressures (pLs) and octanol-air partition coefficients (KOAs). The correlation coefficients indicated that both adsorption onto black carbon and absorption into organic matter were involved in the partition process, but the latter was dominant.

Musks and organochlorine pesticides in breast milk from Shanghai, China: levels, temporal trends and exposure assessment.

The concentrations of musks (polycyclic musks and nitro musks) and traditional organochlorine pesticides (OCPs), including dichlorodiphenyltrichloroethane and its metabolites (DDT, DDE, DDD, and total DDTs), hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCHs) in breast milk collected in Shanghai, China during the period 2006-2010, were determined. The total concentrations ranged from 4.7 to 276.2 (median: 58.4) ng/glipid weight (lw) for musks and from 88.3 to 2532.9 (median: 1003.8) ng/glw for OCPs. 4,4'-DDE (median: 655.4 ng/glw) was the predominant OCP, followed by ß-HCH (median: 172.5 ng/g lw), and HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[γ]-2-benzopyran) (median: 17.7 ng/g lw) was the dominant musk. There was no statistical correlation between total musk concentrations, and HCB, HCHs, DDTs or total OCP concentrations, indicating their different exposure routes and metabolism in humans (p=0.182-0.325). Clear reductions in temporal trends in the levels of DDTs and HCB, especially HCHs (p<0.01) were observed during the sampling period, and the high DDE/DDT ratios in the samples indicated past exposure to DDTs. The relatively high median concentrations of HHCB and HHCB-lactone in 2010 suggested a probably increasing tendency. There were statistically significant influences regarding maternal age and parity on OCP accumulation (p=0.001-0.002), but no significant effect on musks was found (p=0.542-0.919). Musk exposure in neonates via breast milk was 2-3 orders of magnitude lower than suggested provisional tolerable daily intakes (PTDI). The estimated daily intakes for HCB and DDTs were below the PTDI in Canada, however, 56% of those for HCHs exceeded the Canadian PTDI. OCP contamination of breast milk requires further attention.

Coking wastewater treatment plant as a source of polycyclic aromatic hydrocarbons (PAHs) to the atmosphere and health-risk assessment for workers.

PAHs were identified and some of them were determined in the air around a coking wastewater treatment plant (WWTP) using passive air samplers. Seventy seven PAHs were found in the emissions from the degreasing tanks, the aeration tanks and the secondary clarifiers. ∑PAH concentrations within the plant (373.3±27.3-12959.5±685.9 ng/m(3)) were 3-41 times higher compared to the reference sites (315.7±50.2-363.4±77.5 ng/m(3)). The identification of numerous PAHs and high concentrations of these selected ones in the air of the studied sites indicated that the coking WWTP was a new source of atmospheric PAHs. Variations in the PAH pattern were observed in air within the coking WWTP. For example, Flu and Pyr accounted for 35-46% of the total contents at the degreasing tanks, but less than 10% at the hydrolytic tanks. The calculation of the diagnostic ratios suggested that PAHs in the emissions had the source characters of coal combustion. Furthermore, highly elevated PAH concentrations were determined at the degreasing tanks compared to the other tanks (i.e., aeration tanks and secondary clarifiers) and likely associated with their high concentrations in the coking wastewater and increased volatilization at high water temperature. Health risk assessments were carried out by evaluating the inhalation PAH exposure data. The resultant inhalation exposure levels due to TEQ(BaP) for workers ranged from 1.6±0.6 to 71.2±8.2 ng/m(3), and the estimated lung cancer risks were between 0.1×10(-3)±0.1×10(-4) and 5.2×10(-3)±0.5×10(-3), indicating PAHs in the air around the degreasing tanks and the aerobic tanks would have potential lung cancer risk for the operating workers.

Tissue-specific distribution of fatty acids, polychlorinated biphenyls and polybrominated diphenyl ethers in fish from Taihu Lake, China, and the benefit-risk assessment of their co-ingestion.

The fish tissues from four species collected from Taihu Lake, China, were analyzed including dorsal, ventral, and tail muscles, heart, liver, and kidney. The highest and lowest concentrations of fatty acids were respectively observed in livers and muscles. There were significant intraspecies and interspecies differences in the compositions of most fatty acids among muscle, heart, liver, and kidney. All the tissues were generally beneficial for consumption considering fatty acids. People mainly consume the muscle. Hence, the benefits from two polyunsaturated fatty acids, i.e., eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), and risks from PCBs and PBDEs via fish consumption were evaluated by calculating the benefit-risk quotient (BFQ) for the intake of fish muscle containing EPA+DHA vs. PCBs or PBDEs. The BFQ values considering carcinogenic and noncarcinogenic effects for PCBs were ∼3000 and 10 times higher than those of PBDEs via fish consumption to achieve the recommended EPA+DHA intake of 250 mg d(-1), respectively. The results also suggested that the risk consuming the dorsal muscle was generally lower than the ventral and tail muscles.

On-site and off-site atmospheric PBDEs in an electronic dismantling workshop in south China: gas-particle partitioning and human exposure assessment.

Gas samples and total suspended particle during work and off work time were investigated on-site and off-site electronic waste dismantling workshop (I- and O-EWDW), then compared with plastic recycling workshop (PRW) and waste incineration plant (WIP). TSP concentrations and total PBDE were 0.36-2.21 mg/m(3) and 27-2975 ng/m(3) at different workshops, respectively. BDE-47, -99, and -209 were major ∑PBDE congeners at I-EWDW and WIP, while BDE-209 was only dominant congener in PRW and control sites during work time and all sites during off work time. The gas-particle partitioning result was well correlated with the subcooled liquid vapor pressure for all samples, except for WIP and I-EDWD, at park during work time, and residential area during off work time. The predicted urban curve fitted well with measured φ values at O-DEWD during work time, whereas it was slightly overestimated or underestimated for others. Exposure assessment revealed the highest exposure site was I-EDWD.

Contamination, source identification, and risk assessment of polycyclic aromatic hydrocarbons in agricultural soil of Shanghai, China.

The level, distribution, compositional pattern, and possible sources of polycyclic aromatic hydrocarbons (PAHs) in agricultural soil of Shanghai were investigated. The concentrations ranged from 140.7 to 2,370.8 µg kg( -1) for 21 PAHs and from 92.2 to 2,062.7 µg kg( -1) for 16 priority PAHs, respectively. The higher level of PAHs was mainly distributed in the south and west of Shanghai region, and the lower concentration was found in Chongming Island. Generally, the composition pattern of PAHs was characterized with high molecular weight PAHs, the seven possible carcinogenic PAHs accounted for 4.8-50.8% of the total PAHs, and fluoranthene, pyrene, and benzo[b]fluoranthene were the most dominant components in soil samples. The correlation analysis suggested that low molecular weight PAHs and high molecular weight PAHs were originated from different sources and further corroborated that total organic carbon was a key soil property affecting the fate of persistent organic pollutants in the environment. The isomer ratios and principal component analysis indicated that PAHs in the investigated areas were derived primarily from combustion of biomass, coal, and petroleum. Compared to the soil quality standards of the Netherlands, all the target PAHs (except Ant) in most samples exceeded their target values. The Nemerow composite index based on the same soil quality standard showed that 69.4% of the soil samples were heavily polluted. The total BaP(eq) of ten Dutch target PAHs in 72% soil samples were higher than the reference total carcinogenic potency. Therefore, the agricultural soil in Shanghai is suffering from serious PAHs contamination.

Phase partitioning, concentration variation and risk assessment of polybrominated diphenyl ethers (PBDEs) in the atmosphere of an e-waste recycling site.

The daytime and nighttime air samples were collected from an e-waste recycling site in Guiyu (GY) and its upwind and downwind direction sites in Chendian (CD) and Gurao (GR), respectively, during September and December 2005 to determine the phase partitioning, seasonal and diurnal variation of polybrominated diphenyl ethers (PBDEs). The three sites showed similar congener compositions with BDEs-28, -47, -99, -207 and -209 as the dominant congeners. The gas phase contribution ranged from 42.1% ± 17.1% of the total PBDEs in summer to 9.0% ± 8.6% in winter. Partitioning of PBDEs between gas and particulate phases was well correlated with the subcooled liquid vapor pressure (P(L)(0)) for all samples. Both Junge-Pankow adsorption model and K(OA)-based absorption model fitted well the PBDEs data in winter but overestimated the sorption of PBDEs in summer. The mean atmospheric concentrations of BDEs-47 (2748 pg m(-3) in summer and 6146 pg m(-3) in winter) and -99 (1656 pg m(-3) in summer and 4911 pg m(-3) in winter) in GY were much higher than those from other places around the world. Additionally, the time series of PBDEs in GY demonstrated a pronounced diurnal variation pattern, but not CD and GR, where PBDEs appeared partly associated with regional accumulation. Source characterization from local emissions may be the major factor controlling the diurnal variation of PBDEs in GY air. The risk assessment showed that the total daily intakes of BDE-99 in GY was 9.0-34.9 ng kg(-1)-bwd(-1), which is higher than the maximal allowed intake level (0.26 ng kg(-1)-bwd(-1)) with factors of 35-135, indicating possible health risk for GY residents with exposure to PBDEs.

Polybrominated diphenyl ethers in food and associated human daily intake assessment considering bioaccessibility measured by simulated gastrointestinal digestion.

The concentrations of PBDEs in 299 vegetable and animal-based food samples of 31 species, collected in Shanghai, China, and the bioaccessibility of PBDEs in part of the samples were determined. The PBDE concentrations ranged from 0 to 1245.4pgg(-1) with animal-based food containing more PBDEs than vegetables. The bioaccessibility of PBDEs, determined by a method simulating human gastrointestinal digestion process, were from 2.6% to 39.9% in vegetables, and from 5.2% to 105.3% in animal-based food. For animal-based food, good correlations were observed between the bioaccessibility of PBDEs and the fat content, thus the fat content in animal-based food was able to be used to estimate the bioaccessibility of PBDEs. The total daily intake of PBDEs via ingestion of vegetables and animal-based food for an average Shanghai resident was estimated as 13235.7 and 13668.0pg d(-1), respectively, but the amounts available for human absorption were reduced to 2674.4 and 4316.6pgd(-1) after the PBDE bioaccessibility was considered. Finally, the contributions of different food groups to the total daily intake of PBDEs were evaluated. The results revealed that, when not considering the bioaccessibility of PBDEs, vegetables were the leading contributor (49.2%), followed by fish (34.0%). However, the sequence was reversed after the PBDE bioaccessibility was taken into account. The results indicated that human exposure to PBDEs via food ingestion might have been significantly overestimated and the exposure assessment could be misleading if the bioaccessibility of PBDEs was not considered.

Safety assessment of the source water within the Pearl River Delta on the aspect of organochlorine pesticides contamination.

The safety of source water is a noticeable problem in the Pearl River Delta, one of the densely populated areas in China. In this study, 20 individual organochlorine pesticides (OCPs) were investigated in 15 water sources within this area using gas chromatography-electron capture detector, and the hazard risks to human health were assessed in terms of individual OCPs based on daily water consumption according to the standard recommended by the United States Environmental Protection Agency. Results showed that the total OCP concentrations ranged from 2.42 ng l(-1) to 39.52 ng l(-1) during the years 2008 and 2009. The hazard ratios based on both non-cancer and cancer benchmarks were less than 1 for all the water samples, which indicated that individual OCPs posed no risk to human health. However, the risks caused by the combined toxicity of total OCPs in this area should not be ignored.

[Distribution, possible source and ecological risk assessment of polycyclic aromatic hydrocarbons in river sediments from a typical contaminated area].

The concentrations of 16 US EPA PAHs in 37 sediment samples collected from Luqiao were analyzed by isotope dilution gas chromatograph/mass spectrometer (GC/MS), and their distribution characters,sources and ecological risk were further investigated. Each of the 16 PAHs could be detected in all of the sediment samples, the total concentrations of the 16 PAHs in the sediments ranged from 59.3 microg/kg to 3 180 microg/kg,with a mean of 722 microg/kg. The pollution level of PAHs can be categorized as low to moderate when compared with other studies around the world. SigmaPAHs were significantly correlated with TOC (r = 0.699, p < 0.001), indicating that TOC was a key soil property affecting the level and fate of PAHs in sediments. The isomeric ratios and factor analysis revealed that PAHs in the Luqiao sediments were originated from mixed sources, and combustion source was dominant. Six sampling sites had the mean PAH ERL quotient > 1, indicating that some sediments in Luqiao may have potential ecological risk. The toxic benzo[a]pyrene equivalents (TEQ(BaP)) of the 16 PAHs ranged from 3.41 microg/kg to 485 microg/kg, 98.4% of which was contributed by 7 carcinogenic PAHs, indicating that 7 PAHs were the main influential factors to the ecological risk.

Assessment of the bioaccessibility of polybrominated diphenyl ethers in foods and the correlations of the bioaccessibility with nutrient contents.

Bioaccessibility of a contaminant in foods is the fraction of the contaminant mobilized from the food matrices during gastrointestinal digestion. In the present paper, the bioaccessibility of polybrominated diphenyl ethers (PBDEs) in 13 types of foods, including fish, meat, rice, flour, and vegetables, was determined using an in vitro digestion method. The bioaccessibility obtained ranged from 2.6% to 41.3%. It was found that the bioaccessibility of PBDEs exhibited positive correlations with fat and carbohydrate contents and negative correlations with protein and dietary fiber contents in the foods. Fat was the most important factor affecting the bioaccessibility of PBDEs. The mechanism underlying the correlations was discussed in view of partition of PBDEs between liquid and solid phases. To our knowledge, this is the first article systematically investigating the bioaccessibility of PBDEs in foods and demonstrating the influence of the food constituents on the bioaccessibility of PBDEs.

Mutagenicity assessment of produced water during photoelectrocatalytic degradation.

Oilfield produced water was treated by photocatalysis, electro-oxidation, and photoelectrocatalysis, respectively. The chemical composition and toxicity of the raw effluent and treated products were assessed by chemical and mutagenicity analysis. The raw effluent exhibited mutagenic activity in both strains of Salmonella typhimurium. The lowest concentration of the dichloromethane extract capable of inducing a positive response in strains TA98 and TA100 were as low as 4 and 5 microg/plate, respectively. All three technologies could detoxify direct-acting mutagenic organic pollutants efficiently, although they could not completely eliminate mutagenicity in the water after 60 min of treatment. At equivalent doses, photoelectrocatalysis exhibited the greatest capability to reduce genotoxicity, whereas photocatalysis was the least effective and did not cause appreciable change in mutagenicity. The gas chromatography-mass spectrometry (GC-MS) analysis revealed that n-alkanes (259.4 ng/L) and phenolic compounds (2,501.4 ng/L) were the main organic constituents in the oilfield produced water. Thus, the results of both biological and chemical analysis indicate that photoelectocatalysis was the most effective technology for degradation of oilfield wastewater.

Distribution of polycyclic aromatic hydrocarbons in the coastal region off Macao, China: assessment of input sources and transport pathways using compositional analysis.

The coastal region off Macao is a known depositional zone for persistent organic pollutants (POPs) in the Pearl River Delta and Estuary of southern China and an important gateway for the regional contributions of contamination to the globe. This paper presents a comprehensive assessment of the input sources and transport pathways of polycyclic aromatic hydrocarbons (PAHs) found in the coastal sediments of Macao, based on measurements of 48 2-7 ring PAHs and 7 sulfur/oxygenated (S/O) PAH derivatives in 45 sediment, 13 street dust, and 68 aerosol samples. Total sediment PAHs concentrations ranged from 294 to 12741 ng/g, categorized as moderate contamination compared to other regions of Asia and the world. In addition, the PAH compounds appeared to be bound more strongly to aromatics-rich soot particles than to natural organic matter, implying a prevailing atmospheric transport route for PAHs to Macao's coast. Compositional analysis and principal component analysis (PCA) suggested that different classes of PAHs in the coastal sediments of Macao may have been derived from different input sources via various transport pathways. For example, alkylated and S/O PAHs were likely derived from fossil fuel leakage and transported to sediments by both aerosols particles and street runoff. High-molecular-weight parent PAHs were predominantly originated from automobile exhausts and distributed by direct and indirect atmospheric deposition. Low-molecular-weight parent PAHs, on the other hand, may have stemmed from lower temperature combustion and fossil fuel (such as diesel) spillage from ships and boats and were transported to sediments by river runoff or direct discharge as well as by air-water exchange.