Bioaccumulation of novel brominated flame retardants in crucian carp (Carassius auratus): Implications for electronic waste recycling area monitoring.

Bioaccumulation factor (BAF) of pollutants is an important parameter for evaluating their bioaccumulation potential and an important indicator for evaluating their environmental risks. However, little study exits on the BAF of novel brominated flame retardants (NBFRs). The present study determined 17 NBFRs in 24 water samples in dissolved phase and 93 crucian carp samples collected from an electronic waste recycling site in northern China, in order to examine their contamination, distribution and bioaccumulation. The results showed that the targeted NBFRs were widely detectable in the dissolved phase and crucian carps. In dissolved phase, allyl 2,4,6-tribromophenyl ether (ATE) had the highest detectable rate (100%) and concentration (mean: 1.3 ± 0.62 ng/L), but in crucian carp, hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) was the one with the highest detectable rate (89%) and concentration (mean: 16 ± 9.2 ng/g wet weight (ww)) among all 17 NBFRs. The discharge and water solubility of NBFRs determined their concentration in the dissolved phase, while the concentration of NBFRs in crucian carp was the results of their discharge and food exposure. The estimated BAFs exceeded 5000 L/kg for petabromoethylbenzene (PBEB), pentabromotoluene (PBT), HCDBCO, pentabromobenzyl acrylate (PBBA), 1,2,3,4,5-pentabromobenzene (PBBZ), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), hexabromobenzene (HBBZ), and α-1,2,5,6-tetrabromocyclooctane (α-TBCO), suggesting that these compounds were above the hazard standard of bioaccumulation. Although the BAFs of 2,3,5,6-tetrabromo-p-xylene (p-TBX), 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), α-/ß-tetrabromoethylcyclohexane (α-/ß-TBECH) and ATE were less than 5000, the potential of bioaccumulation cannot be ignored. The log BAF of tested NBFRs showed a pattern of first increasing and then decreasing with the increase of log KOW, the water solubility of NBFRs, the exposure to fish, the uptake and depuration of fish were the key factor to this pattern. To our knowledge, the BAF values of the most of NBFRs calculated in this study were not reported in the published work previously.

PM2.5 exposure promotes asthma in aged Brown-Norway rats: Implication of multiomics analysis.

Children are disproportionately represented among those who suffer asthma, which is a kind of chronic airway inflammation. Asthma symptoms might worsen when exposed to the air pollutant particulate matter 2.5 (PM2.5). However, it is becoming more prevalent among older adults, with more asthma-related deaths occurring in this pollution than in any other age group, and symptoms caused by asthma can reduce the quality of life of the elderly, whose asthma is underdiagnosed due to physiological factors. Therefore, in an effort to discover a therapy for older asthma during exposure to air pollution, we sought to ascertain the effects of pre-exposure (PA) and persistent exposure (PAP) to PM2.5 in aged asthma rats. In this study, we exposed aged rats to PM2.5 at different times (PA and PAP) and established an ovalbumin-mediated allergic asthma model. The basic process of elderly asthma caused by PM2.5 exposure was investigated by lung function detection, enzyme-linked immunosorbent assay (ELISA), histopathology, cytology, cytokine microarray, untargeted metabolomics, and gut microbiota analysis. Our findings demonstrated that in the PA and PAP groups, exposure to PM2.5 reduced lung function and exacerbated lung tissue damage, with varying degrees of effect on immunoglobulin levels, the findings of a cytological analysis, cytokines, and chemokines. The PA and PAP rats had higher amounts of polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, 2-methylNaphthalene, 1-methylNaphthalene and flourene. Moreover, exposure to PM2.5 at different times showed different effects on plasma metabolism and gut microbiota. Bioinformatics analysis showed a strong correlation between PAHs, cytokines, and gut microbiota, and PAHs may cause metabolic disorders through the gut microbiota. These findings point to a possible mechanism for the development of asthma in older people exposure to PM2.5 that may be related to past interactions between PAHs, cytokines, gut microbiota, and plasma metabolites.

Characterization of Volatile Profiles and Correlated Contributing Compounds in Pan-Fried Steaks from Different Chinese Yellow Cattle Breeds through GC-Q-Orbitrap, E-Nose, and Sensory Evaluation.

This study focused on characterizing the volatile profiles and contributing compounds in pan-fried steaks from different Chinese yellow cattle breeds. The volatile organic compounds (VOCs) of six Chinese yellow cattle breeds (bohai, jiaxian, yiling, wenshan, xinjiang, and pingliang) were analyzed by GC-Q-Orbitrap spectrometry and electronic nose (E-nose). Multivariate statistical analysis was performed to identify the differences in VOCs profiles among breeds. The relationship between odor-active volatiles and sensory evaluation was analyzed by partial least square regression (PLSR) to identify contributing volatiles in pan-fried steaks of Chinese yellow cattle. The results showed that samples were divided into two groups, and 18 VOCs were selected as potential markers for the differentiation of the two groups by GC-Q-Orbitrap combined multivariate statistical analysis. YL and WS were in one group comprising mainly aliphatic compounds, while the rest were in the other group with more cyclic compounds. Steaks from different breeds were better differentiated by GC-Q-Orbitrap in combination with chemometrics than by E-nose. Six highly predictive compounds were selected, including 3-methyl-butanal, benzeneacetaldehyde, 2-ethyl-6-methyl-pyrazine, 2-acetylpyrrole, 2-acetylthiazole, and 2-acetyl-2-thiazoline. Sensory recombination difference and preference testing revealed that the addition of highly predictive compounds induced a perceptible difference to panelists. This study provides valuable data to characterize and discriminate the flavor profiles in pan-fried steaks of Chinese yellow cattle.

Comparison of super-mini-PCNL and flexible ureteroscopy for the management of upper urinary tract calculus (1-2 cm) in children.

OBJECTIVES: To retrospectively evaluate the efficacy and safety of super-mini percutaneous nephrolithotomy (SMP) and retrograde intrarenal surgery (RIRS) for children with upper urinary tract calculus (1-2 cm). PATIENTS AND METHODS: Children with upper urinary tract calculus (1-2 cm) who underwent the SMP or RIRS were enrolled in this study. Patients were divided into two groups: group SMP, 36 patients; and group RIRS, 25 patients. Patients were evaluated with KUB radiography or CT after 1 month. The collected data were analyzed. RESULTS: The mean stone size was 14.18 mm in group SMP, and 14.00 mm in group RIRS (p = 0.812). Group RIRS compared to group SMP showed longer operating time [76.3 vs 53.9 min (p = 0.002)], and postoperative hospital stay [4.2 vs 2.9 days (p = 0.011)]. The overall stone-free rate (SFR) was 94.4% for group SMP, and 60.0% for group RIRS in 1 month after operation (p = 0.001). The re-treatment rate was significantly higher in group RIRS compared to group SMP [20.0% vs 0.0% (p = 0.009)]. The complication rate was 5.6%, and 24.0% for groups SMP, and RIRS, respectively (p = 0.036). CONCLUSIONS: SMP was more effective than RIRS to obtain a better SFR, less re-treatment rate, and complication rate in children with upper urinary tract calculus (1-2 cm).

Assessment bioaccumulation factor (BAF) of methyl siloxanes in crucian carp (Carassius auratus) around a siloxane production factory.

Methyl siloxanes are identified as emerging persistent toxic compounds and the ecological environment risks of these compounds have been caused of great concern worldwide. In this study, the concentrations of methyl siloxanes were reported in dissolved water and crucian carp around a methyl siloxane production factory located in Liaoning Province, Northeast China. D4, D5, D6, D7, L4, L5 and L6 were detectable both in dissolved water and crucian carp. The total concentrations of 7 methyl siloxanes (Σ7MS) were 14 ± 6.3 ng/L in dissolved water and 43 ± 22 ng/g ww in crucian carp, respectively. D5 has the highest concentration both in dissolved water (5.5 ± 3.5 ng/L) and crucian carp (17 ± 11 ng/g ww). Based on the monitoring values, bioaccumulation factor (BAF) of these compounds were calculated. Significant bioaccumulation potential was observed for D4 (BAF = 5900 ± 3500 L/kg) based on the bioaccumulation criteria suggested by USEPA and EU (BAF > 5000 L/kg). To our understanding, this is the first report of BAF values of methyl siloxane in field study, which will provide important support for further assessment of bioaccumulation of these compounds.

Occurrence of Phthalates in Bottled Drinks in the Chinese Market and Its Implications for Dietary Exposure.

Ubiquitous occurrences of phthalic acid esters (PAEs) or phthalates in a variety of consumer products have been demonstrated. Nevertheless, studies on their occurrence in various types of bottled drinks are limited. In this study, fifteen PAEs were analyzed in six categories of bottled drinks (n = 105) collected from the Chinese market, including mineral water, tea drinks, energy drinks, juice drinks, soft drinks, and beer. Among the 15 PAEs measured, DEHP was the most abundant phthalate with concentrations ranging from below the limit of quantification (LOQ) to 41,000 ng/L at a detection rate (DR) of 96%, followed by DIBP (DR: 88%) and DBP (DR: 84%) with respective concentration ranges of below LOQ to 16,000 and to 4900 ng/L. At least one PAE was detected in each drink sample, and the sum concentrations of 15 PAEs ranged from 770 to 48,004 ng/L (median: 6286 ng/L). Significant differences with respect to both PAE concentrations and composition profiles were observed between different types of bottled drinks. The median sum concentration of 15 PAEs in soft drinks was over five times higher than that detected in mineral water; different from other drink types. Besides DEHP, DBIP, and DBP, a high concentration of BMEP was also detected in a tea drink. The estimated daily dietary intake of phthalates (EDIdrink) through the consumption of bottled drinks was calculated based on the concentrations measured and the daily ingestion rates of bottled drink items. The EDIdrink values for DMP, DEP, DIBP, DBP, BMEP, DAP, BEEP, BBP, DCP, DHP, BMPP, BBEP, DEHP, DOP, and DNP through the consumption of bottled mineral water (based on mean concentrations) were 0.45, 0.33, 12.5, 3.67, 2.10, 0.06, 0.32, 0.16, 0.10, 0.09, 0.05, 0.81, 112, 0.13, and 0.20 ng/kg-bw/d, respectively, for Chinese adults. Overall, the EDIdrink values calculated for phthalates through the consumption of bottled drinks were below the oral reference doses suggested by the United States Environmental Protection Agency (U.S. EPA).

Distribution, seasonal trends, and lung cancer risk of atmospheric polycyclic aromatic hydrocarbons in North China: A three-year case study in Dalian city.

Atmospheric monitoring data of polycyclic aromatic hydrocarbons (PAHs) over a three-year period were collected from an urban site in Dalian, northeast China. The status of PAHs in the atmosphere in Dalian were evaluated by assessing concentration levels, congener profiles, seasonal trends, primary source, inhalation exposure and the risk of developing lung cancer risk. Average concentrations were recorded for 53 PAHs (95 ± 40 ng/m3), 16 EPA priority PAHs (68 ± 33 ng/m3), 26 alkylated PAHs (17 ± 7.6 ng/m3) and 4 high-molecular-weight (302 Da) PAHs (1.3 ± 1.3 ng/m3). Atmospheric PAH concentrations in winter were almost twice as high as those recorded in the summer, possibly due to enhanced local emissions and long-range transport of atmospheric PAHs during the winter. PAH congeners were dominated by phenatherene, fluoranthene, pyrene and fluorene, accounting for 46.0% of total ∑53PAH concentrations. Ship/vehicle emission and mixed combustion were identified as the main sources of PAHs using diagnostic PAH concentration ratios and principal component analysis-multiple linear regression. Benzo(a)pyrene toxicity equivalent concentration had an average content of 32 ± 37 ng/m-3 over the sampling period, with dibenzo(a,h)anthracene (50.7%) and dibenzo(a,l)pyrene (26.4%) being the largest contributors. The risk of developing lung cancer due to inhalation exposure to outdoor PAHs was calculated at 12.0‰ using the overall population attributable fraction (PAF). Our results estimate that, due to PAH exposure in Dalian, the average excess lung cancer risk during a person's lifetime is 35.7 cancer cases per one million inhabitants.

PAHs in Chinese atmosphere Part II: Health risk assessment.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in atmosphere, which attracted more attentions due to their influence on human health. In this study, a national scale cancer risk (CR) assessment with atmospheric PAHs were conducted based on one year monitoring program at 11 cities across China. The annual mean concentrations of benzo[a]pyrene (BaP) and BaP equivalency (BaPeq) were 4.56 ± 7.78 ng/m3 and 8.45 ± 14.1 ng/m3, respectively, which were both higher than the new ambient air quality standards of China (GB 3095-2012, 1 ng/m3). Concentrations of BaP and BaPeq in northern Chinese cities were almost 2 times higher than those in southern Chinese cities. The CR values induced by the dermal contact exposure were two orders of magnitude higher than that by the inhalation exposure. Children and adults were the most sensitive age groups with the dermal contact exposure and the inhalation exposure to atmospheric PAHs, respectively. For the total CR values, 99.7% of its values were higher than the reference level of 10-6. No significant difference of the total CR values was observed between northern Chinese and southern Chinese cities for children and adults. In order to quantify the uncertainties of CR assessment, Monte Carlo Simulation was applied based on the specific distributions of the exposure factors cited from the Exposure Factors Handbook of Chinese Population. The results indicated that almost 90% probability of the total CR values were higher than 10-6, indicating potential cancer risk. Sensitive analysis indicated that atmospheric concentration, outdoor exposure fraction, particle amount adhered to skin, and cancer slope factor should be carefully considered in order to increase the accuracy of CR assessment with PAHs in atmosphere.

Trophic transfer of cyclic methyl siloxanes in the marine food web in the Bohai Sea, China.

Trophic transfer of cyclic methyl siloxanes (CMS) in aquatic ecosystems is an important criterion for assessing its environmental risks. This study researched the trophic transfer of four CMS (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and tetradecamethylcycloheptasiloxane (D7)) in marine food web from zooplankton up to seabirds in the Chinese Bohai Sea. In the zooplankton-invertebrate-fish-seabird based food web, the significant trophic magnifications were found for D4 to D6 (D4: R2 = 0.040, p < 0.05, D5: R2 = 0.26, p < 0.0001, D6: R2 = 0.071, p < 0.001), and the significant trophic dilution was found for D7 (R2 = 0.026 and p < 0.05). The trophic magnification factors (TMF) for D4 to D7 were 1.7 (95% confidence interval: 1.1-2.6), 3.5 (2.5-5.0), 1.8 (1.3-2.6), and 0.63 (95% CI: 0.40-0.99) respectively. In the zooplankton-invertebrate-fish based food web, both significant trophic magnification for D5 (R2 = 0.16, p < 0.0001, TMF = 3.0) and significant trophic dilution for D7 (R2 = 0.073, p < 0.01, TMF = 0.4) were found, but for D4 and D6, the trophic magnifications were not significant (D4: R2 = 0.010, p = 0.23, D6: R2 = 0.010, p = 0.23). The trophic transfer of the legacy contaminant BDE-47 and BDE-99 were also conducted as the benchmark chemicals and significant positive correlation was found. As far as we know, this is the first research on the trophic transfer of CMS in the zooplankton-invertebrate-fish-bird food chain which provided new insight of these compounds in the area.

Bioaccumulation of Methyl Siloxanes in Common Carp (Cyprinus carpio) and in an Estuarine Food Web in Northeastern China.

Despite the high production volume and widespread use of methyl siloxanes, limited studies have been conducted to investigate the bioconcentration, biomagnification, and trophic magnification potentials of these substances. In the present study, bioconcentration factors (BCFs) of methyl siloxanes were determined with common carp exposed at environmental relevant levels for 32 days. BCF of octamethylcyclotetrasiloxane (D4) was estimated as 6197 L/Kg, indicating strong bioconcentration potential in the common carp. To assess the food chain transfer of methyl siloxanes, 12 aquatic invertebrates and vertebrates species were collected from a food web in Shuangtaizi estuary in northeastern China and concentrations of methyl siloxanes in these species were determined with gas chromatography mass spectrometry. Trophic magnification factors (TMFs) of decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and linear siloxanes (L7-10) were significantly greater than 1 in one food chain selected, which suggest trophic magnification potentials of these methyl siloxanes. Biomagnification factors of D4-D6 and L7-L10 from planktons to Japanese snapping shrimp were greater than 1, indicating biomagnification potentials of these methyl siloxanes from the prey to predator. This is the first study to investigate the bioaccumulation behaviors of methyl siloxanes by coupling BCF and BMF with TMF.

Occurrence and Source Effect of Novel Brominated Flame Retardants (NBFRs) in Soils from Five Asian Countries and Their Relationship with PBDEs.

This paper presents the first comprehensive survey of 19 novel brominated flame retardants (NBFRs) in soil samples collected among five Asian countries. High variability in concentrations of all NBFRs was found in soils with the geometric mean (GM) values ranging from 0.50 ng/g dry weight (dw) in Vietnam to 540 ng/g dw in the vicinity of a BFR manufacturer in China. In urban, rural, and background locations, the GM concentrations of ∑19NBFRs decreased in the order of Japan > South Korea > China > India > Vietnam. Correlations among different NBFR compounds were positive and statistically significant (p < 0.05), suggesting that they originate from similar sources. Evidence for simultaneous application between polybrominated diphenyl ethers (PBDEs) and NBFRs were also noted. Principal component analysis of NBFR concentrations revealed specific pollution sources for different NBFRs coming from urban, BFR-related industrial, and e-waste sites. For the first time, this study demonstrates a "point source fractionation effect" for NBFRs and PBDEs. The concentrations of all NBFRs and PBDEs were negatively and significantly correlated with the distance from BFR-related industrial and e-waste regions. Positive and significant correlation between population density and NBFR concentrations in soils was identified. Our study revealed that the primary sources effects were stronger than the secondary sources effects in controlling the levels and distribution of NBFRs and PBDEs in soils in these five Asian countries.

Distribution, Fate, Inhalation Exposure and Lung Cancer Risk of Atmospheric Polycyclic Aromatic Hydrocarbons in Some Asian Countries.

A large-scale monitoring program, the Asia Soil and Air Monitoring Program (Asia-SAMP), was conducted in five Asian countries, including China, Japan, South Korea, Vietnam, and India. Air samples were collected using passive air samplers with polyurethane foam disks over four consecutive 3-month periods from September 2012 to August 2013 to measure the seasonal concentrations of 47 polycyclic aromatic hydrocarbons (PAHs), including 21 parent and 26 alkylated PAHs, at 176 sites (11 background, 83 rural, and 82 urban). The annual concentrations of total 47 PAHs (∑47PAHs) at all sites ranged from 6.29 to 688 ng/m(3) with median of 82.2 ng/m(3). Air concentrations of PAHs in China, Vietnam, and India were greater than those in Japan and South Korea. As expected, the air concentrations (ng/m(3)) were highest at urban sites (143 ± 117) followed by rural (126 ± 147) and background sites (22.4 ± 11.4). Significant positive correlations were found between PAH concentrations and atmosphere aerosol optical depth. The average benzo(a)pyrene equivalent concentration (BaPeq) was 5.61 ng/m(3). It was estimated that the annual BaPeq concentrations at 78.8% of the sampling sites exceeded the WHO guideline level. The mean population attributable fraction (PAF) for lung cancer due to inhalation exposure to outdoor PAHs was on the order 8.8‰ (0.056-52‰) for China, 0.38‰ (0.007-3.2‰) for Japan, 0.85‰ (0.042-4.5‰) for South Korea, 7.5‰ (0.26-27‰) for Vietnam, and 3.2‰ (0.047-20‰) for India. We estimated a number of lifetime excess lung cancer cases caused by exposure to PAHs, which the concentrations ranging from 27.8 to 2200, 1.36 to 108, 2.45 to 194, 21.8 to 1730, and 9.10 to 720 per million people for China, Japan, South Korea, Vietnam, and India, respectively. Overall, the lung cancer risk in China and Vietnam were higher than that in Japan, South Korea, and India.

Polybrominated Diphenyl Ethers (PBDEs) in Surface Soils across Five Asian Countries: Levels, Spatial Distribution, and Source Contribution.

A total of 23 polybrominated diphenyl ether (PBDE) congeners were measured in soil samples collected in areas with no known point source [urban/rural/background (U/R/B) sites] and in areas with known point source [brominated flame retardant (BFR)-related industrial sites (F sites) and e-waste recycling sites (E sites)] across five Asian countries. The highest PBDE concentrations were found in BFR-related industrial and e-waste recycling sites. The concentrations of PBDEs in U/R/B sites decreased in the following order: urban > rural > background sites. Total PBDE concentrations were dominated by BDE-209, while BDE-17, -85, -138, -191, -204, and -205 were the least abundant compounds. In both urban sites and rural sites, the mean concentrations of total PBDEs (∑23BDEs) in soils decreased in the following order: Japan > China > South Korea > India > Vietnam. The concentrations of PBDEs in soils were comparable with those reported in other studies. Among the three commercial PBDE mixtures, relatively large contributions of commercial penta-BDE were observed in Vietnam, whereas deca-BDE was the dominant form in mixtures contributing from 55.8 ± 2.5 to 100.0 ± 1.2% of the total PBDEs in soils collected from other four countries. Regression analysis suggested that local population density (PD) is a good indicator of PBDEs in soils of each country. Significant and positive correlation between soil organic content and PBDE level was observed in Chinese soil for most nondeca-BDE homologues with their usage stopped 10 years ago, indicating its important role in controlling the revolatilization of PBDEs from soil and changing the spatial trend of PBDE in soil from the primary distribution pattern to the secondary distribution pattern, especially when primary emission is ceased.

Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in the coastal seawater, surface sediment and oyster from Dalian, Northeast China.

A total of 46 polycyclic aromatic hydrocarbons (PAHs, 21 parent and 25 alkylated) were determined in seawater, surface sediment and oyster from coastal area of Dalian, North China. The concentration of Σ46PAHs in seawater, sediment, and oyster were 136-621 ng/L, 172-4700 ng/g dry weight (dw) and 60.0-129 ng/g wet weight (ww) in winter, and 65.0-1130 ng/L, 71.1-1090 ng/g dw and 72.8-216 ng/g ww in summer, respectively. High PAH levels were found in industrial area both in winter and summer. Selected PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism and the results indicate that surface sediment from all sampling sites have a low to medium ecotoxicological risk. Daily intake of PAHs via oyster as seafood by humans were estimated and the results indicated that oyster intake would not pose a health risk to humans even 30 days after a oil spill accident near by. Water-sediment exchange analysis showed that, both in winter and summer, the fluxes for most high molecular weight PAHs were from seawater to sediment, while for low molecular weight PAHs, an equilibrium was reached between seawater and sediment.

Trophic transfer of methyl siloxanes in the marine food web from coastal area of Northern China.

Methyl siloxanes, which belong to organic silicon compounds and have linear and cyclic structures, are of particular concern because of their potential characteristic of persistent, bioaccumulated, toxic, and ecological harm. This study investigated the trophic transfer of four cyclic methyl siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and tetradecamethylcycloheptasiloxane (D7)) in a marine food web from coastal area of Northern China. Trophic magnification of D4, D5, D6, and D7 were assessed as the slope of lipid equivalent concentrations regressed against trophic levels of marine food web configurations. A significant positive correlation (R = 0.44, p < 0.0001) was found between lipid normalized D5 concentrations and trophic levels in organisms, showing the trophic magnification potential of this chemical in the marine food web. The trophic magnification factor (TMF) of D5 was estimated to be 1.77 (95% confidence interval (CI): 1.41-2.24, 99.8% probability of the observing TMF > 1). Such a significant link, however, was not found for D4 (R = 0.14 and p = 0.16), D6 (R = 0.01 and p = 0.92), and D7 (R = -0.15 and p = 0.12); and the estimated values of TMFs (95% CI, probability of the observing TMF > 1) were 1.16 (0.94-1.44, 94.7%), 1.01 (0.84-1.22, 66.9%) and 0.85 (0.69-1.04, 48.6%) for D4, D6, and D7, respectively. The TMF value for the legacy contaminant BDE-99 was also estimated as a benchmark, and a significant positive correlation (R = 0.65, p < 0.0001) was found between lipid normalized concentrations and trophic levels in organisms. The TMF value of BDE-99 was 3.27 (95% CI: 2.49-4.30, 99.7% probability of the observing TMF > 1), showing the strong magnification in marine food webs. To the best of our knowledge, this is the first report on the trophic magnification of methyl siloxanes in China, which provided important information for trophic transformation of these compounds in marine food webs.

Prediction of gas/particle partition quotients of Polybrominated Diphenyl Ethers (PBDEs) in north temperate zone air: an empirical approach.

Gas/particle (G/P) partitioning process is an important factor governing the transport and fate of chemicals in the atmosphere. Based on a large dataset of more than 700 pairs of air samples in gaseous and particulate phases with a wide ambient temperature range of 60°C from -22°C to +38°C obtained from our Chinese POPs Soil and Air Monitoring Program, Phase 2 (China-SAMP-II), we investigated G/P partitioning behavior of polybrominated diphenyl ether (PBDEs) in Chinese air. We derived for the first time empirical equations to predict the values of slopes and intercepts for both subcooled-liquid-vapor-pressure (PL)-based and octanol-air-partition-coefficient (KOA)-based models as functions of temperature, and thus predicted partition quotient (KP) without assuming an equilibrium status and free of artifacts. These equations have been successfully applied to predict the values of KP for PBDEs in air of China and other countries in the north temperate zone (NTZ) and also at an Arctic site in East Greenland, and our results matched the monitoring data well at background, rural, urban, and suburban sites, but not at e-waste sites due to the unpredictable PBDE emissions at these sites. Our equations predicted that the ranges of slopes were 0.02-0.82 for logKP-logKOA plots and -0.82 to -0.02 for logKP-logPL plots at temperatures ranged of 60°C from -22°C to +38°C. Our new KOA-based equation was compared with the Harner-Bidleman equation that was derived at a condition of equilibrium, and the results indicated that our new equation has a better performance than the Harner-Bidleman equation in describing G/P partitioning behavior of PBDEs in air as functions of logKOA. We also found for the first time that the G/P partitioning of PBDE congeners would become saturated in the particulate phase respect to the gas phase if the ambient temperature is low enough. A criterion to classify the equilibrium and nonequilibrium status for PBDEs was also established using logKOA. The study presented in this paper provides a useful tool for environmental scientists in both monitoring and modeling research on G/P partitioning behavior for PBDEs in air.

Temperature dependence of the rain-gas and snow-gas partition coefficients for nearly a thousand chemicals.

Compared to the particle-gas partition coefficients (KPG), the rain-gas (KRG) and snow-gas (KSG) partition coefficients are also essential in studying the environmental behavior and fate of chemicals in the atmosphere. While the temperature dependence for the KPG have been extensively studied, the study for KRG and KSG are still lacking. Adsorption coefficients between water surface-air (KIA) and snow surface-air (KJA), as well as partition coefficients between water-air (KWA) and octanol-air (KOA) are vital in calculating KRG and KSG. These four basic adsorption and partition coefficients are also temperature-dependent, given by the well-known two-parameters Antoine equation logKXY = AXY + BXY/T, where KXY is the adsorption or partition coefficients, AXY and BXY are Antoine parameters (XY stand for IA, JA, WA, and OA), and T is the temperature in Kelvin. In this study, the parameters AXY and BXY are calculated for 943 chemicals, and logKXY can be estimated at any ambient temperature for these chemicals using these Antoine parameters. The results are evaluated by comparing these data with published experimental and modeled data, and the results show reasonable accuracy. Based on these coefficients, temperature-dependence of logKRG and logKSG is studied. It is found that both logKRG and logKSG are linearly related to 1/T, and Antoine parameters for logKRG and logKSG are also estimated. Distributions of the 943 chemicals in the atmospheric phases (gas, particle, and rain/snow), are illustrated in a Chemical Space Map. The findings reveal that, at environmental temperatures and precipitation days, the dominant state for the majority of chemicals is the gaseous phase. All the AXY and BXY values for logKSG, logKRG, and basic adsorption and partition coefficients, both modeled by this study and collected from published work, are systematically organized into an accessible dataset for public utilization.

Polybrominated diphenyl ethers in air across China: levels, compositions, and gas-particle partitioning.

Air samples were concurrently collected using high volume air samplers for 24 h every week from September 2008 to August 2009 at 15 sites (11 urban, 1 suburban, and 3 background/rural) across China. Twelve polybrominated diphenyl ether (PBDE) congeners (BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183, and -209) were measured. Total PBDE concentrations (∑12PBDEs) in air (gas + particle phases) were in the range of 11.0-838 pg m(-3) with a mean of 232 ± 72 (mean ± SE) pg m(-3). The site with the highest concentration was Guangzhou (838 ± 126 pg m(-3)), followed by Beijing (781 ± 107 pg m(-3)). Significant positive correlations were found between PBDEs levels and urban population (R = 0.69, P < 0.05) and gross industrial output values (R = 0.87, P < 0.001) as well. BDE-209 was the dominating congener with the contribution of 64 ± 23% to ∑12PBDEs, followed by BDE-47(8 ± 8%) and -99(6 ± 5%) at all urban and suburban sites. At background/rural sites, however, BDE-47 was the dominating congener, followed by BDE-99, together accounting for 52 ± 21% of ∑12PBDEs, while BDE-209 was only 11 ± 2%. It was found that PBDEs at the 15 sites showed a primary distribution and fractionation pattern. This study produced more than 700 pairs of air samples in gaseous and particulate phases with a wide temperature range of ∼60 °C, providing a good opportunity to investigate gas-particle partitioning for individual PBDE congeners. The results of gas-particle partitioning analysis for PBDEs using both subcooled-liquid-vapor pressure (PL)-based and octanol-air partition coefficient (KOA)-based models indicated that PBDEs in air at all sampling sites had not reached equilibrium because the slope values (mO) in the KOA-based equation and the opposite slope values (mP) in the PL-based equation at all 15 sampling sites were less than 1. It also found that both mO and -mP were significantly and positively correlated with the annual average temperatures of sampling sites and also significantly and negatively correlated with the mole masses of PBDE congeners, indicating a general trend that the higher the temperature at the sampling site and the lower the mole mass of the PBDE congeners are, the closer to the equilibrium the congeners approach and vice versa. To our knowledge, this is the first study to report the correlations of the slope values for both the KOA-based and PL-based equations with temperatures at sampling sites and mole masses for individual PBDE congeners.

Characterization of polycyclic aromatic hydrocarbons in concurrently monitored surface seawater and sediment along Dalian coast after oil spill.

Polycyclic aromatic hydrocarbons (PAHs) were measured in concurrently sampled surface seawater and sediment collected at 20 sites around Dalian, China 50 days after an oil spill accident. The concentrations of total PAHs ranged from 15 to 160 ng L(-1) in seawater, and from 64 to 2100 ng g(-1) dry weight in surface sediment. The spatial trends of PAHs in seawater, but not in sediment, showed a significant negative correlation with the distance from the oil spill site, indicating a strong source of PAHs from oil spill place to the surrounding seawater. The similar profiles for PAH composition in both crude oil and seawater could indicate that oil spill caused PAHs concentration in seawater, but not in sediment. Analysis of water-sediment exchange of PAHs showed that the direction of the net flux of PAHs was from sediment to seawater for most priority PAHs, and from water to sediment for a few HWM-PAHs.