Brominated and organophosphate flame retardants along a sediment transect encompassing the Guiyu, China e-waste recycling zone.

e-Waste recycling using crude techniques releases a complex, yet incompletely characterized mixture of hazardous materials, including flame retardants (FRs), to the environment. Their migration downstream and the associated risks also remain undocumented. We examined 26 FRs (18 brominated (BFRs: 12 polybrominated diphenyl ether (PBDE) congeners, plus 6 alternatives) and 8 organophosphate esters (OPEs)) in surficial sediments of the Lian River. Sampling encompassed the river's origin, through the Guiyu e-waste recycling zone, to its mouth, as well as associated tributaries. OPE exceeded BFR concentrations in most sediments, despite their far greater water solubilities. Among OPEs, tris(1-chloro-2-propyl) phosphate dominated upstream, but shifted to triphenyl phosphate in Guiyu and downstream sediments. For PBDEs, Deca-BDE dominated upstream, but Penta-BDE prevailed in Guiyu and at many downstream sites. Among emerging alternative BFRs, decabromodiphenyl ethane dominated upstream, transitioning to 1,2-bis(2,4,6,-tribromophenoxy)ethane in Guiyu sediments. Penta-BDE (BDE-47 + -99, 668-204,000 ng g-1, ∑PBDEs 2280-287,000 ng g-1), tetrabromobisphenol A (2,720-41,200 ng g-1), 1,2-bis(2,4,6,-tribromophenoxy)ethane (222-9870 ng g-1) and triphenyl phosphate (4260-1,710,000 ng g-1, OPEs 6010-2,120,000 ng g-1) concentrations in Guiyu sediments were among the highest reported in the world to date. The continuing dominance of these e-waste indicative FRs in sediments downstream of Guiyu suggested that FR migration from Guiyu occurred. Hazard quotients >1.0 indicated that the extreme sediment concentrations of individual FRs posed ecological risks in most Guiyu reach and downstream areas. Simultaneous exposure to multiple FRs likely increased risks. However, risks may be mediated if FRs were associated with strong sorbents, e.g. carbon black from burned debris, hydrophobic polymer fragments, or resided as additives within polymer fragments.

Polychlorinated biphenyls and their hydroxylated metabolites in the serum of e-waste dismantling workers from eastern China.

A number of studies have reported on the exposure of e-waste dismantling workers to significantly high concentrations of halogenated organic pollutants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers. Such exposure can have adverse health effects. However, little information on the metabolites of these contaminants exists. In this study, we investigated PCBs levels and their hydroxylated metabolites (OH-PCB) in the serum of e-waste workers in Taizhou in eastern China. Our results indicate elevated PCB and OH-PCB levels in the serum of the workers, with medians of 443.7 and 133.9 ng/g lw, respectively. Tri- to hexachlorinated PCB congeners were the dominant homologue groups in all of the samples. 4-OH-CB107 was the predominant homologue among the hydroxylated metabolites, accounting for 88.9% of the total OH-PCB concentrations. While dietary sources (e.g., fish) appear to be an important route for PCB accumulation in non-occupational exposure groups, exposure via ingestion of house dust and inhalation of pollutants derived from the recycling of PCB-containing e-wastes may primarily contribute to the high body burden observed in the occupational groups. Since we found concentrations of metabolites higher than those of their parent compounds, further studies need to pay more attention to their bioaccumulation and toxicity.

[Light Absorption Properties of Water-Soluble Organic Carbon (WSOC ) Associated with Particles in Autumn and Winter in the Urban Area of Guangzhou].

Light absorption properties of water-soluble organic carbon (WSOC) were investigated in the urban area of Guangzhou. The fine particulate matter (PM2.5) and size-segregated samples were collected in September and December of 2014 and January of 2015. The variation of absorption with wavelength of WSOC was characterized by the absorption Angström exponent (AAEabs). The AAE values of WSOC in PM2.5 were 3.72 ± 0.41 in autumn and 3.91 ± 0.70 in winter, which were lower than those in Beijing and north America. The mass absorption efficiency (MAE) of WSOC at 365 nm wavelength was 0.52 m² · g⁻¹ in autumn and 0.92 m² · g⁻¹ in winter, exhibiting distinct variations between autumn and winter. In winter, the MAEwsoc values exhibited a decreasing trend with increasing particle size, and all size-segregated MAE(WSOC) values in autumn were lower than those in winter, particularly for the particles < 0.95 µm, suggesting more contribution of the secondary formation to WSOC. Comparing the MAE values of elemental carbon (EC) and WSOC, it could be found that the contribution of WSOC to the light extinction of particles couldn't be ignored when the particles were mainly emitted from primary sources.

LINE-1 gene hypomethylation and p16 gene hypermethylation in HepG2 cells induced by low-dose and long-term triclosan exposure: The role of hydroxyl group.

Triclosan (TCS), a frequently used antimicrobial agent in pharmaceuticals and personal care products, exerts liver tumor promoter activities in mice. Previous work showed high-dose TCS (1.25-10µM) induced global DNA hypomethylation in HepG2 cells. However, whether or how tumor suppressor gene methylation changed in HepG2 cells after low-dose and long-term TCS exposure is still unknown. We investigate here the effects and mechanisms of DNA methylation of global DNA(GDM), repetitive genes, and liver tumor suppressor gene (p16) after exposing HepG2 cells to low-dose TCS (0.625-5nM)for two weeks using HPLC-MS/MS, Methylight, Q-MSP, Pyrosequencing, and Massarray methods. We found that low-dose TCS exposure decreased repetitive elements LINE-1 methylation levels, but not global DNA methylation, through down-regulating DNMT1 (DNA methyltransferase 1) and MeCP2 (methylated DNA binding domain) expression, and up-regulating 8-hydroxy-2-deoxyguanosine (8-OHdG) levels. Interestingly, low-dose TCS elevated p16 gene methylation and inhibited p16 expression, which were not observed in high-dose (10µM) group. Meanwhile, methyl-triclosan could not induce these two types of DNA methylation changes, suggesting the involvement of hydroxyl in TCS-mediated DNA methylation changes. Collectively, our results suggested low concentrations of TCS adversely affected HepG2 cells through DNA methylation dysregulation, and hydroxyl group in TCS played an important role in the effects. This study provided a better understanding on hepatotoxicity of TCS at environmentally relevant concentrations through epigenetic pathway.

Airborne polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and dechlorane plus (DP) in concentrated vehicle parking areas.

This study investigated polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and dechlorane plus (DP) in air around three concentrated vehicle parking areas (underground, indoor, and outdoor) in a metropolitan of South China. The parking areas showed higher concentrations of PBDEs, PBDD/Fs, and DP than their adjacent urban area or distinct congener/isomer profiles, which indicate their local emission sources. The highest PBDE and DP concentrations were found in the outdoor parking lot, which might be related to the heating effect of direct sunlight exposure. Multi-linear regression analysis results suggest that deca-BDEs without noticeable transformation contributed most to airborne PBDEs in all studied areas, followed by penta-BDEs. The statistically lower anti-DP fractions in the urban area than that of commercial product signified its degradation/transformation during transportation. Neither PBDEs nor vehicle exhaust contributed much to airborne PBDD/Fs in the parking areas. There were 68.1-100 % of PBDEs, PBDD/Fs, and DP associated with particles. Logarithms of gas-particle distribution coefficients (K ps) of PBDEs were significantly linear-correlated with those of their sub-cooled vapor pressures (p Ls) and octanol-air partition coefficients (K OAs) in all studied areas. The daily inhalation doses of PBDEs, DP, and PBDD/Fs were individually estimated as 89.7-10,741, 2.05-39.4, and 0.12-4.17 pg kg(-1) day(-1) for employees in the parking areas via Monte Carlo simulation.

Passive sampling of polybrominated diphenyl ethers in indoor and outdoor air in Shanghai, China: seasonal variations, sources, and inhalation exposure.

Ninety-seven seasonal, passive indoor and outdoor air samples were collected in Shanghai to study polybrominated diphenyl ethers (ΣPBDEs, 16 congeners including BDE-209), their concentrations, composition profiles, seasonal variations, influencing factors, emission sources, and human inhalation exposure. In summer, median indoor concentrations of Σ 15 PBDEs (excluding BDE-209) were 82 pg m(-3) in offices and 30 pg m(-3) in homes, ∼3 times the winter concentrations. The average summer concentration of 130 pg m(-3) BDE-209 in homes was higher than that in offices (which was 90 pg m(-3)); in winter, home and office concentrations were similar (46 and 47 pg m(-3), respectively). For outdoor air, the median concentration of Σ 15 PBDEs in summer (12 pg m(-3)) was twice the winter concentration (6 pg m(-3)), while the summer median concentration of BDE-209 (398 pg m(-3)) was half the winter concentration (794 pg m(-3)). Higher concentrations of Σ 15 PBDEs indoors compared with outdoors showed that the lower brominated BDEs found were mainly from indoor sources. Meanwhile, the much lower indoor concentration of BDE-209 compared with the outdoors showed that BDE-209 came mainly from outdoor sources. The data set also indicated that electric/electronic appliances were the main sources of indoor ΣPBDEs, and old appliances emitted more lower brominated BDEs, while industrial emissions should be the main source of the outdoor BDE-209. Median daily human exposures to Σ 15 PBDEs and BDE-209 through inhalation were estimated to be 0.23 and 1.73 ng day(-1) in winter and 0.65 and 2.28 ng day(-1) in summer for adults. The human inhalation exposure to ΣPBDEs (3.44 ng day(-1) for adults and 1.33 ng day(-1) for toddlers) was comparable to that from eating contaminated fish for both toddlers and adults in Shanghai.

Absorption and recovery of n-hexane in aqueous solutions of fluorocarbon surfactants.

n-Hexane is widely used in industrial production as an organic solvent. As an industrial exhaust gas, the contribution of n-hexane to air pollution and damage to human health are attracting increasing attention. In the present study, aqueous solutions of two fluorocarbon surfactants (FSN100 and FSO100) were investigated for their properties of solubilization and dynamic absorption of n-hexane, as well as their capacity for regeneration and n-hexane recovery by thermal distillation. The results show that the two fluorocarbon surfactants enhance dissolution and absorption of n-hexane, and their effectiveness is closely related to their concentrations in solution. For low concentration solutions (0.01%-0.30%), the partition coefficient decreases dramatically and the saturation capacity increases significantly with increasing concentration, but the changes for both are more modest when the concentration is over 0.30%. The FSO100 solution presents a smaller partition coefficient and a greater saturation capacity than the FSN100 solution at the same concentration, indicating a stronger solubilization for n-hexane. Thermal distillation is a feasible method to recover n-hexane from these absorption solutions, and to regenerate them. With 90sec heating at 80-85°C, the recovery of n-hexane ranges between 81% and 85%, and the regenerated absorption solution maintains its original performance during reuse. This study provides basic information on two fluorocarbon surfactants for application in the treatment of industrial n-hexane waste gases.

The occurrence and removal of organophosphate ester flame retardants/plasticizers in a municipal wastewater treatment plant in the Pearl River Delta, China.

The occurrence, distribution and main removal pathway of seven widely used organophosphate esters (OPs) in a municipal wastewater treatment plant (WWTP) located in the Pearl River Delta were investigated. Their daily discharge load into the Pearl River via effluent was also estimated. All the target analytes were detected in wastewater, suspended particle and dewatered sludge, with tri-n-butyl phosphate (TBP) and tris(2-butoxyethyl) phosphate (TBEP) as the main components. The total concentrations of TBP and TBEP were 21271.8 ng L(-1) and 4349.4 ng L(-1), 3105.1 ng L(-1) and 494.5 ng L(-1) in influent wastewater and final effluent, respectively. These results indicated that non-chlorinated OPs were removed efficiently in the WWTP, while chlorinated OPs passed through the WWTP unchanged due to their resistance to current wastewater treatment technology. Approximate 91.4 g of non-chlorinated OPs and 23.4 g of chlorinated OPs per day were discharged into the Pearl River via effluent, 2.4 g of non-chlorinated OPs and 0.6 g of chlorinated OPs entered the environment following sludge disposal.

Determination of polybrominated diphenyl ethers in soils and sediment of Hanfeng Lake, Three Gorges.

As ubiquitous organic contaminants, polybrominated diphenyl ethers (PBDEs) were evaluated to explore the impacts of the water level fluctuating zone (WLFZ) on organic pollutant behavior and the retention mechanism of organic pollutants in the bank-WLFZ-water system of Hanfeng Lake in the Three Gorges region of China. The mean concentrations of total PBDEs were 103, 75.2, and 568 ng g(-1) dry wt for bank soils, WLFZ soils, and sediment samples, respectively. Except for sampling sites S1 and S2, the levels of PBDEs decreased in the order of sediment>WLFZ soil > bank soil, suggesting that PBDEs were transferred from bank soil to WLFZ soil and finally deposited in the sediment. Decabromodiphenyl ethers (deca-BDEs) were the predominant congener in the study area, comprising 93.8% to 98.3% of the total PBDEs. Greater photolytic degradation of deca-BDEs was suggested in bank soils based on a higher relative abundance of octa- and nona-BDEs than in WLFZ soils and sediment. This may have occurred because deca-BDEs in bank soils have relatively longer sunlight exposure than in WLFZ soils and sediment due to the annual alternation of water storage and drainage in the catchments of the Three Gorges Reservoir. More in-depth investigations of contaminants in bank-WLFZ-water systems are needed due to the large areas of WLFZ created by the construction of the Three Gorges Dam and their importance to the balance of aquatic ecosystems.

Distribution of polybrominated diphenyl ethers and HBCD in sediments of the Hunhe River in Northeast China.

Forty surface sediment samples from the Hunhe River in Northeast China were evaluated for contamination by polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). The results showed that decabromodiphenyl ether (BDE-209) was the predominant congener, accounting for >98 % of PBDEs in all sediment. The concentrations of BDE-209 and HBCD ranged from 3.96 to 327 ng/g dry weight and 0.05 to 25.8 ng/g dry weight, respectively, suggesting that BDE-209 was more widely applied in the study area. The mean concentrations of BDE-209 and HBCD in the downstream portion of the Hunhe River (BDE-209 148 ng/g dry weight and HBCD 3.74 ng/g dry weight) were found to be relatively higher than those in the upstream portion of the Hunhe River and the Dahuofang Reservoir, revealing an association with municipal sewage and industrial effluent received from the cities of Fushun and Shenyang. γ-HBCD was the most abundant diastereoisomer of all three analyzed HBCD isomers; however, marked elevations of α-HBCD were also found in most sediment samples. Surprisingly, the relative abundance (mean 38%) of α-HBCD in sediment from the upstream portion of the Hunhe River was significantly higher (p < 0.006, t test) than those in Dahuofang Reservoir (mean 24%). Moreover, the severe heavy metal contamination associated with the frequent mining activities in this region was tentatively suggested as being responsible for the increased levels of α-HBCD.

Absorption of gaseous toluene in aqueous solutions of some kinds of fluorocarbon surfactant.

A self-designed device was applied to treat a simulated exhaust gas loaded with toluene by aqueous solutions of five kinds of fluorocarbon surfactant (FS-3100, FS-22, FSN-100, FSO-100 and FSG) under the controlled laboratory conditions. The simulated exhaust gas is generated by a mixture of clean air and toluene vapor, and its toluene concentration can be controlled by changing the volume ratio of the inlet air to the vapor. Two mass transfer methods: liquid-liquid transfer and gas-liquid transfer, were compared for their toluene saturation capacities of these absorbent solutions, and it was found that more toluene was dissolved by the liquid-liquid transfer than by the gas-liquid transfer. According to the saturation capacities of these absorbent solutions and their Henry's Constants, FSO-100 is the best absorbent to treat the simulated exhaust gas and was selected for further experiments. The FSO-100 absorbent solution with a concentration of 0.1 % shows an efficient absorption to the simulated exhaust gas, with a toluene saturation capacity of 4.2 mg/g. Heating distillation (90- 95 oC) is highly efficient to recover toluene from the FSO-100 absorbent solution as well as regenerate it. A toluene recovery of about 85 % was achieved. The regenerated absorption solution can keep its initial toluene absorption capacity during the reuse.

Enantiomeric composition of polycyclic musks in sediments from the Pearl River and Suzhou Creek.

Due to differences in stereostructure, enantiomeric compositions and enantiomeric ratios (ERs) of chiral compounds can be used to discriminate environmental processes such as abiotic and biotic degradation/transformation. In this study, the ERs of two chiral polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), were investigated in the sediments of Zhujiang River and Dongjiang River in the Pearl River Delta (PRD), as well as in those of Suzhou Creek in Shanghai City. The results indicated that ER cis of HHCB varied significantly, ranging from 1.09 to 1.53 and 1.40 to 1.48 in the PRD and Suzhou Creek samples, respectively, whereas ER trans of HHCB exhibited limited variation, ranging from 0.98 to 1.10 and 0.98 to 1.05 for Pearl River and Suzhou Creek samples, respectively. In addition, ERs of AHTN varied substantially from 1.10 to 1.34 and 1.17 to 1.28 in the PRD and Suzhou Creek, respectively. These results suggest that HHCB in the sediment in the study area underwent biotic degradation and the preferential biotransformation isomer was (4R,7S)-HHCB, while AHTN simultaneously underwent a certain degree of biotic degradation/transformation.

The toxicity of sediments from Taihu Lake evaluated by several in vitro bioassays.

In vitro bioassays are useful techniques for the determination of biological effects in sediment samples containing complex mixtures of contaminants. In this study, 28 surface sediment samples from Taihu Lake, East China, were collected for toxicity assessment using a battery of in vitro bioassays. The battery included a two-hybrid yeast bioassay for estrogenic and thyroidal effects, the H4IIE rat hepatoma cell bioassay for aryl hydrocarbon (Ah) receptor (Ah-agonists)-mediated effects as measured by ethoxyresorufin-O-deethylase (EROD) activity, and the SOS/umu bioassay for genotoxic effects. Toxicities were expressed as 17ß-estradiol equivalents (EEQs), T3 (3,5,3'-triiodothyronine) equivalents (T3-EQs), 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs), and induction ratios (IRs) of ß-galactosidase activity. The results showed that total estrogenic effects in sediment samples ranged from 0.0011 to 12.4 pg EEQ/g sediment [dry weight (d.w.)], the thyroidal effects ranged from 0.35 to 24.8 pg T3-EQ/g sediment (d.w.), the Ah-agonist effects varied from 2.70 to 37.8 pg TEQ/g sediment (d.w.), and the weight of soil required for the extracts to lead to a positive result (IR 2.0) in the SOS/umu bioassay was between 1.98 and 15.3 mg (d.w.) per well. Significantly positive correlations were only found between lgT3-EQs and lgEEQs, which indicated similar spatial distributions of estrogenic and thyroidal effects in Taihu Lake. These results suggested that the applied battery of in vitro bioassays represented an efficient (fast and cost-effective) screening system for the identification of emerging contaminants in Taihu Lake and provided meaningful information for further analysis and risk evaluation.

Spatial distribution of heavy metal contamination in soils near a primitive e-waste recycling site.

The total concentrations of 12 heavy metals in surface soils (SS, 0-20 cm), middle soils (MS, 30-50 cm) and deep soils (DS, 60-80 cm) from an acid-leaching area, a deserted paddy field and a deserted area of Guiyu were measured. The results showed that the acid-leaching area was heavily contaminated with heavy metals, especially in SS. The mean concentrations of Ni, Cu, Zn, Cd, Sn, Sb and Pb in SS from the acid-leaching area were 278.4, 684.1, 572.8, 1.36, 3,472, 1,706 and 222.8 mg/kg, respectively. Heavy metal pollution in the deserted paddy field was mainly concentrated in SS and MS. The average values of Sb in SS and MS from the deserted paddy field were 16.3 and 20.2 mg/kg, respectively. However, heavy metal contamination of the deserted area was principally found in the DS. Extremely high concentrations of heavy metals were also observed at some special research sites, further confirming that the level of heavy metal pollution was very serious. The geoaccumulation index (Igeo) values revealed that the acid-leaching area was severely polluted with heavy metals in the order of Sb > Sn > Cu > Cd > Ni > Zn > Pb, while deserted paddy field was contaminated predominately by metals in the order of Sb > Sn > Cu. It was obvious that the concentrations of some uncommon contaminants, such as Sb and Sn, were higher than principal contaminants, such as Ni, Cu, Zn and Pb, suggesting that particular attention should be directed to Sn and Sb contamination in the future research of heavy metals in soils from e-waste-processing areas. Correlation analysis suggested that Li and Be in soils from the acid-leaching area and its surrounding environment might have originated from other industrial activities and from batteries, whereas Ni, Cu, Zn, Cd, Pb, Sn and Sb contamination was most likely caused by uncontrolled electronic waste (e-waste) processing. These results indicate the significant need for optimisation of e-waste-dismantling technologies and remediation of polluted soil environment.

Urinary monohydroxylated metabolites of polycyclic aromatic hydrocarbons in children living in city and rural residences in Southern China.

Urinary 2-hydroxynaphthalene, 2-hydoxyfluorene, 9-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenz[a]pyrene concentrations in 179 randomly selected voluntary students were determined in the Southern China, aged 14-16 and living in four areas with different levels of polycyclic aromatic hydrocarbons (PAHs) in soil, water and ambient air. The excretion of 1-hydroxypyrene is significantly higher in students of the urban than in students of the rural, while there are no significant differences of urinary 2-hydroxynaphthalene, 2-hydoxyfluorene and 9-hydroxyphenanthrene between urban and rural children. Mean concentrations of 1-hydroxypyrene (0.54-0.80 µmol/mol creatinine) in the study are much higher than those in the children of Denmark, Germany, Spain, USA, Korea, Japan and Taiwan, and a little higher than those in the children of Ukraine and Thailand. Urinary 2-hydroxynaphthalene concentrations in the study are a little higher than those in the children of USA, and similar to that in non-occupational exposure residences in Korea. Urinary 9-hydroxyphenanthrene concentrations in China are much higher than those in the children of USA. Differences between children with smoking parents and non-smoking parents are not significant in the study.

Distribution of heavy metal pollution in sediments from an acid leaching site of e-waste.

The spatial distribution, bioavailability, potential risks and emission sources of 12 heavy metals in sediments from an acid leaching site of e-waste were investigated. The results showed that the sediments from the acid leaching site were significantly contaminated with Cu, Zn, Cd, Sn, Sb and Pb, especially in the middle sediments (30-50 cm), with average concentrations of 4820, 1260, 10.7, 2660, 5690 and 2570 mg/kg, respectively. Cu, Cd and Pb were mainly present in the non-residual fractions, suggesting that the sediments from the acid leaching site may exert considerable risks. Mn, Ni, Zn, Sn and Sb were predominantly associated with the residual fraction. Despite their low reactivity and bioavailability, uncommon pollutants, such as Sn and Sb, may exert environmental risks due to their extremely elevated total concentrations. All of these results indicate that there is an urgent need to control the sources of heavy metal emission and to remediate contaminated sediments. CAPTURE ABSTRACT: In addition to Ni, Cu, Zn, Cd and Pb, the sediments from an acid leaching site in Guiyu were heavily polluted with uncommon heavy metal pollutants, such as Sn and Sb.

Comparison of elemental and black carbon measurements during normal and heavy haze periods: implications for research.

Studies specifically addressing the elemental carbon (EC)/black carbon (BC) relationship during the transition from clean-normal (CN) air quality to heavy haze (HH) are rare but have important health and climate implications. The present study, in which EC levels are measured using a thermal-optical method and BC levels are measured using an optical method (aethalometer), provides a preliminary insight into this issue. The average daily EC concentration was 3.08 ± 1.10 µg/m(3) during the CN stage but climbed to 11.77 ± 2.01 µg/m(3) during the HH stage. More importantly, the BC/EC ratio averaged 0.92 ± 0.14 during the CN state and increased to 1.88 ± 0.30 during the HH state. This significant increase in BC/EC ratio has been confirmed to result partially from an increase in the in situ light absorption efficiency (σap) due to an enhanced internal mixing of the EC with other species. However, the exact enhancement of σap was unavailable because our monitoring scheme could not acquire the in situ absorption (bap) essential for σap calculation. This reveals a need to perform simultaneous measurement of EC and bap over a time period that includes both the CN and HH stages. In addition, the sensitivity of EC to both anthropogenic emissions and HH conditions implies a need to systematically study how to include EC complex (EC concentration, OC/EC ratio, and σap) as an indicator in air quality observations, in alert systems that assess air quality, and in the governance of emissions and human behaviors.

Determination of ten hexabromocyclododecane diastereoisomers using two coupled reversed-phase columns and liquid chromatography/tandem mass spectrometry.

RATIONALE: Hexabromocyclododecanes (HBCDs) are raising concern due to their potential persistence, bioaccumulation and toxicity. Apart from the widely reported isomers α-, ß-, γ-HBCD, other HBCD diastereoisomers such as δ-HBCD have been also recently found in environmental media and biota. These newly reported diastereoisomers might give more insight into the degradation and biotransformation of HBCDs. METHODS: A reversed-phase C18 column coupled to a C8 column was used to improve the chromatographic resolution. A gradient mobile phase consisting of methanol, acetonitrile, and water, as well as tandem mass spectrometry parameters, were optimized. Ten HBCD diastereoisomers were finally determined by liquid chromatography/tandem mass spectrometry in multiple reaction monitoring mode with negative electrospray ionization. RESULTS: Eight of the ten HBCDs could be chromatographically separated by using the coupled reversed-phase columns. Results of the method validation indicate high reproducibility and good sensitivity. The limit of detection ranged from 0.4 to 0.8 pg, and the relative standard deviations of intra- and inter-day injections ranged from 1.8 to 5.1% and from 2.7 to 9.5%, respectively. The developed method was further applied to the analysis of HBCDs in HBCD commercial products and soil samples. δ-, η-, θ-, and ε-HBCD were detected in commercial products and soil samples. CONCLUSIONS: The present study revealed that δ-, η-, θ-, and ε-HBCD might occur ubiquitously in environmental media and biota. These newly reported diastereoisomers may help us to better understand the fate and transformation of HBCDs in the environment.

Biological monitoring of environmental exposure to polycyclic aromatic hydrocarbons in subjects living in the area of recycling electronic garbage, in Southern China.

The study was undertaken to evaluate the environmental exposure to polycyclic aromatic hydrocarbons in subjects living in the area of recycling electronic garbage in Southern China and research the influence of environment smoke tobacco (EST) to people through active and passive smoking. Urinary concentrations of 2-hydroxynaphthalene, 2-hydoxyfluorene, 9-hydroxyphenanthrene, and 1-hydroxypyrene were determined in 141 randomly selected voluntary residents aged 13 to 81 years in two polycyclic aromatic hydrocarbon (PAH)-exposed groups, two control groups, and an EST research group. The concentrations of 2-hydroxynaphthalene, 2-hydoxyfluorene, 9-hydroxyphenanthrene, and 1-hydroxypyrene in PAH-exposed groups are significantly higher (p<0.05) than those of control groups. Mean value of 1-hydroxypyrene in the residents living in the area of recycling electronic garbage (1.1 µmol/mol creatinine) is a little higher than those of iron foundry workers, automobile repair workers, and firefighters. Mean value of 2-hydroxynaphthalene (11.3 µmol/mol creatinine) is much higher than that of shipyard and aircraft maintenance and much lower than some occupational exposure, such as coking batteries, sorting department, and distillation department in coking plant. Some metabolites of PAHs (PAHm) are significantly elevated through active and passive smoking, while the influence of EST to other PAHm is not statistically significant. 2-Hydroxynaphthalene, 2-hydoxyfluorene, 9-hydroxyphenanthrene, and 1-hydroxypyrene in the urine of smokers are, respectively, 3.9, 1.9, 1.4, and 1.9 times to those of nonsmokers. In nonsmokers, passive smokers excreted 1.1, 1.5, 1.9, and 1.5 times of 2-hydroxynaphthalene, 2-hydoxyfluorene, 9-hydroxyphenanthrene, and 1-hydroxypyrene compared to nonpassive smokers.

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.