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.

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.

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.

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.

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.

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.

Effects of benzene and its metabolites on global DNA methylation in human normal hepatic L02 cells.

Benzene is an important industrial chemical that is also widely present in cigarette smoke, automobile exhaust, and gasoline. It is reported that benzene can cause hematopoietic disorders and has been recognized as a human carcinogen. However, the mechanisms by which it increases the risk of carcinogenesis are only partially understood. Aberrant DNA methylation is a major epigenetic mechanism associated with the toxicity of carcinogens. To understand the carcinogenic capacity of benzene, experiments were designed to investigate whether exposure to benzene and its metabolites would change the global DNA methylation status in human normal hepatic L02 cells and then to evaluate whether the changes would be induced by variation of DNA methyltransferase (DNMT) activity in HaeIII DNMT-mediated methylation assay in vitro. Our results showed that hydroquinone and 1,4-benzoquinone could induce global DNA hypomethylation with statistically significant difference from control (p < 0.05), but no significant global DNA methylation changes were observed in L02 cells with benzene, phenol, and 1,2,4-trihydroxybenzene exposure. Benzene metabolites could not influence HaeIII DNMT activity except that 1,4-benzoquinone shows significantly inhibiting effect on enzymatic methylation reaction at concentrations of 5 µM (p < 0.05). These results suggest that benzene metabolites, hydroquinone, and 1,4-benzoquinone can disrupt global DNA methylation, and the potential epigenetic mechanism by which that global DNA hypomethylation induced by 1,4-benzoquinone may work through the inhibiting effects of DNMT activity at 10 µM (p < 0.05).

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.

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.

Compound-specific stable carbon isotope analysis of galaxolide enantiomers in sediment using gas chromatography/isotope ratio monitoring mass spectrometry.

RATIONALE: Both chiral analysis and compound-specific stable carbon isotope analysis have limitations when applied to environmental research. However, the combination of these two techniques might overcome their respective limitation and give more insight into the enantioselective fate and source apportionment of chiral organic contaminants. METHODS: After Soxhlet extraction and clean-up, sediment extracts were further pre-concentrated using normal-phase preparative high-performance liquid chromatography to isolate sufficient quantities of highly purified galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran; HHCB). The enantiomeric fractions and stable carbon isotopes of the HHCB were determined using gas chromatography/mass spectrometry (GC/MS) and GC/isotope ratio mass spectrometry (IRMS). RESULTS: The method was validated by analysis of the enantiomeric fractions and the stable carbon isotope ratios of the HHCB standard at each step of the pre-concentration procedure, and no significant enantiomeric and isotopic fractionation was found. The sediment sample was further used to test the developed method, and it was shown that the HHCB enantiomers in the sediment sample exhibited significantly different δ(13) C values (-33.03 to -24.57‰) and a slight enantiomeric fractionation (0.507 and 0.490) from a HHCB standard reference compound (-26.50 to -26.21‰ for δ(13) C values, and 0.519 and 0.497 for enantiomeric fractions). CONCLUSIONS: This work offers a novel approach to elucidating the sources and the abiotic or biological transformation processes of HHCB in the environment and will offer a perspective for assessing the environment fate of any chiral organic compound.

PI3K/Akt pathway mediates Nrf2/ARE activation in human L02 hepatocytes exposed to low-concentration HBCDs.

We investigated the effects of hexabromocyclododecanes (HBCDs) at environmentally relevant concentrations on human L02 hepatocytes and explored possible underlying molecular mechanism(s), focusing on functional interactions between the phosphatidylinositol 3-kinase/protein kinase B (PI3K/Akt) and nuclear factor-erythroid 2-related factor 2/antioxidant response element (Nrf2/ARE) pathways. The results showed that low concentrations of HBCDs could stimulate cell proliferation in a "DNA-dependent protein kinase catalytic subunit" (DNA-PKcs)-dependent manner, increase protein levels and nuclear translocation of transcription factor Nrf2, and upregulate expression of its target gene heme oxygenase-1 (HO-1). Electrophoretic mobility-shift assays (EMSAs) showed that ARE was a prominent element for HO-1 induction after low-concentration HBCDs exposure. The relationship between PI3K/Akt pathway and Nrf2/HO-1 axis was demonstrated by the finding that pretreatment with PI3K inhibitors (wortmannin, LY294002) attenuated the upregulation of Nrf2 expression induced by HBCDs exposure. Furthermore, knock-down of DNA-PKcs through small interfering RNA blocked Nrf2/HO-1 axis activation in L02 cells exposed to low-concentration HBCDs. Moreover, DNA-PKcs and phosphorylated Akt at Ser(473) proved to be crucial in regulating the Nrf2-ARE pathway. Thus, the PI3K/Akt pathway is essential in regulating Nrf2-ARE pathway activation in L02 cells induced by low-concentration HBCDs.

Trace elements in fish from Taihu Lake, China: levels, associated risks, and trophic transfer.

Concentrations of eight trace elements [iron (Fe), manganese (Mn), zinc (Zn), chromium (Cr), mercury (Hg), cadmium (Cd), lead (Pb), and arsenic (As)] were measured in a total of 198 samples covering 24 fish species collected from Taihu Lake, China, in September 2009. The trace elements were detected in all samples, and the total mean concentrations ranged from 18.2 to 215.8 µg/g dw (dry weight). The concentrations of the trace elements followed the sequence of Zn>Fe>Mn>Cr>As>Hg>Pb>Cd. The measured trace element concentrations in fish from Taihu Lake were similar to or lower than the reported values in fish around the world. The metal pollution index was used to compare the total trace element accumulation levels among various species. Toxabramis swinhonis (1.606) accumulated the highest level of the total trace elements, and Saurogobio dabryi (0.315) contained the lowest. The concentrations of human non-essential trace elements (Hg, Cd, Pb, and As) were lower than the allowable maximum levels in fish in China and the European Union. The relationships between the trace element concentrations and the δ(15)N values of fish species were used to investigate the trophic transfer potential of the trace elements. Of the trace elements, Hg might be biomagnified through the food chain in Taihu Lake if the significant level of p-value was set at 0.1. No biomagnification and biodilution were observed for other trace elements.

Trace elements in animal-based food from Shanghai markets and associated human daily intake and uptake estimation considering bioaccessibility.

The concentrations of four human essential trace elements [iron (Fe), manganese (Mn), zinc (Zn), chromium (Cr)] and non-essential elements [cadmium (Cd), lead (Pb), arsenic (As), and mercury (Hg)] in eighteen animal-based foods including meat, fish, and shellfish collected from markets in Shanghai, China, were analyzed, and the associated human daily intake and uptake considering bioaccessibility were estimated. The mean concentration ranges for eight trace elements measured in the foods were 3.98-131µgg(-1) for Fe, 0.437-18.5µgg(-1) for Mn, 5.47-53.8µgg(-1) for Zn, none detected-0.101µgg(-1) for Cr, 2.88×10(-4)-2.48×10(-2)µgg(-1) for Cd, 1.18×10(-3)-0.747µgg(-1) for Pb, none detected-0.498µgg(-1) for As, and 8.98×10(-4)-6.52×10(-2)µgg(-1) for Hg. The highest mean concentrations of four human essential elements were all found in shellfish. For all the trace elements, the observed mean concentrations are mostly in agreement with the reported values around the world. The total daily intake of trace elements via ingestion of animal-based food via an average Shanghai resident was estimated as 7371µgd(-1) for the human essential elements and 13.0µgd(-1) for the human non-essential elements, but the uptake decreased to 4826µgd(-1) and 6.90µgd(-1), respectively, after trace element bioaccessibility was considered. Livestock and fish for human essential and non-essential elements, respectively, were the main contributor, no matter whether the bioaccessibility was considered or not. Risk estimations showed that the intake and uptake of a signal trace element for an average Shanghai resident via ingestion animal-based foods from Shanghai markets do not exceed the recommended dietary allowance values; consequently, a health risk situation is not indicated.

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.

Polycyclic aromatic hydrocarbons and organochlorine pesticides in fish from Taihu Lake: their levels, sources, and biomagnification.

The investigation of biomagnification of polycyclic aromatic hydrocarbons (PAHs) and endosulfan, an organochlorine pesticide (OCP) and a new persistent organic pollutant, has been limited in freshwater food chains. The objective of the present study was to investigate the levels with focus on the sources and biomagnification of PAHs and OCPs in fish from Taihu Lake, China. In 193 samples of 24 species investigated, the concentrations ranged from 289 to 9 500 ng/g lipid weight (lw) for PAHs, and from 121 to 904 ng/g lw for OCPs, indicating that the fish in the lake was moderately contaminated. The PAHs mainly originated from both unburned petroleum and combustion of fossil fuels, and the OCPs from aged residues. It was unlikely that most of the PAHs and OCPs were biodiluted through the food chain because their trophic magnification factors were higher than one nevertheless the P-values >0.05. Aldrin, dieldrin, p,p'-DDE, p,p'-DDD, and endosulfan sulfate were significantly biomagnified through the food chain.

Chlorinated and brominated dibenzo-p-dioxins and dibenzofurans in surface sediment from Taihu Lake, China.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.

Levels and distribution of synthetic musks and polycyclic aromatic hydrocarbons in sludge collected from Guangdong Province.

The levels and distribution of six polycyclic musks, three nitromusks and 15 polycyclic aromatic hydrocarbons (PAHs) were investigated in sludge collected from 19 municipal wastewater treatment plants (WWTPs) in six cities in Guangdong Province, China. PAHs were detected in all of the sludge samples, and the levels of the total 15 PAHs ranged from 177.2-4421.8 µg/kg dry weight (dw). Four polycyclic musks, 4-acetyl-1,1-dimethyl-6-tert-butylindan (ADBI), 6-acetyl-1,1,2,3,3,5-hexamethylindan (AHMI), 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-tetrahydro naphthalene (AHTN), were found in these samples. The total concentrations of polycyclic musks varied from 794.4-12960.3 µg/kg dw, with HHCB and AHTN being the main components. Of the three nitromusks, 2,6-dinitro-3-methoxy-4-tert- butyl - toluene (MA) was only found in one sludge sample at the limit of detection (LOD) level, while 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (Musk xylene, MX) and 4-acetyl-1-tert-butyl-3,5-dimethyl-2,6-dinitrobenzene (Musk ketone, MK) were found at levels ranging from the LOD to 65.8 µg/kg dw and LOD to 172.7 µg/kg dw, respectively, in most of the sludge samples. The PAHs, polycyclic musks and nitro musks were also shown to have various distribution patterns, possibly due to their different wastewater sources and wastewater treatment technology.

Hexabromocyclododecanes in surface soils from E-waste recycling areas and industrial areas in South China: concentrations, diastereoisomer- and enantiomer-specific profiles, and inventory.

Hexabromocyclododecanes (HBCDs) are raising concern because of their potential persistence, bioaccumulation, and toxicity. In this study, we investigated the concentrations, diastereoisomer- and enantiomer-specific profiles, and mass inventories of HBCDs in 90 surface soils from two e-waste recycling areas (Qingyuan, Guiyu) and from industrial areas in South China. The mean concentrations of total HBCDs in the surface soils ranged from 0.22 to 0.79 and from 0.31 to 9.99 ng/g dw for two surrounding e-waste recycling sites and industrial areas, respectively. The highest total HBCD concentration (284 ng/g dw) was found at the e-waste recycling site in Qingyuan, while total HBCD levels fell dramatically with increasing distance from the recycling site, suggesting that the e-waste recycling activities were an important source of HBCDs. The diastereoisomer profiles in 75 of the 90 soil samples differed from those of the commercial products. The mean enantiomeric fraction values for α-, ß-, and γ-HBCDs in soils ranged from 0.503(0.010) to 0.507(0.003), 0.494(0.003) to 0.506(0.009), and 0.502(0.003) to 0.511(0.006), respectively, suggesting that there was no stereoselective transformation of the three diastereoisomers. The mass inventories of HBCDs gave preliminarily estimates of 3.42 kg and 1.84 tonnes for the e-waste recycling areas and industrial areas, respectively. It is notable that the diasteroisomer and enantiomer profiles of this study failed to distinguish definitely that the isomeric transformation occurred during the product processing or in the environmental matrix. Further laboratory studies on abiotic and biotic transformation are needed to clarify this issue.

Harmonizing aerosol carbon measurements between two conventional thermal/optical analysis methods.

Although total carbon (TC) can be consistently quantified by various aerosol carbon measurement methods, the demarcation of TC into organic carbon (OC) and elemental carbon (EC) has long been inconsistent. The NIOSH and IMPROVE protocols are most widely used for thermal/optical analysis (TOA), but current knowledge rests in the description that the NIOSH protocol usually gives lower EC values than does the IMPROVE protocol. This study seeks to explore the possibility of quantitatively linking the difference between the two TOA protocols. Residential coal-burning samples that had been collected and analyzed following the NIOSH protocol in previous studies were directly reanalyzed following the IMPROVE protocol for this study. A comparison of each pair of NIOSH and IMPROVE EC values reveals the dynamic relation between the two protocols, which can be expressed as a regression equation, y=(1-x)/(1+4.86x2) (R2=0.96), where the independent x is the EC/TC ratio R(EC/TC) for the IMPROVE protocol, and the dependent y is the difference between IMPROVE and NIOSH REC/TC relative to IMPROVE REC/TC. This regression equation may be the first effort in formulating the relationship between the two TOA protocols, and it is very helpful in harmonizing inconsistent TOA measurements, for example, source characterization, ambient monitoring, and atmospheric modeling.

Identification of monochloro-nonabromodiphenyl ethers in the air and soil samples from south China.

Several studies have indicated that mixed brominated/chlorinated organic compounds could be formed during the thermal process such as the incineration of municipal solid waste and open burning of unregulated e-waste at recycling areas. In this study, air particles and soils from e-waste recycling areas, as well as outdoor and indoor air particles from urban Guangzhou, were collected and pooled for the identification of mixed chlorinated/brominated diphenyl ethers (PXDEs). Three monochloro-nonabromo diphenyl ethers (Cl-nonaBDEs), including 6'-Cl-BDE-206, 5'-Cl-BDE-207, and/or 4'-Cl-BDE-208, were first structurally identified in these air and soil samples. The identification was done by comparison of retention times in chromatograms of pure reference compounds and environmental samples, as well as by comparison with full-scan mass spectra data in electron capture negative ionization mode. Because of their similar physical-chemical properties, 4'-Cl-BDE-208 and 5'-Cl-BDE-207 absolutely coeluted, even on a nonpolar DB-5 column. Further investigation is still needed to clarify these findings. Nevertheless, the results indicated that Cl-nonaBDEs would occur in various environmental matrices. Because the replacement of Br by Cl will change the physical-chemical properties of PBDE analogues, environmental occurrence, fate, and transport, the potential toxicity of PXDEs should be investigated.