Polybrominated diphenyl ethers in surface sediments from principal watersheds of Shanghai, China: levels, distribution, influencing factors, and risk assessment

Fourteen and 17 sediment samples were collected from three main rivers of Shanghai in July and November, respectively. Eight polybrominated diphenyl ether (PBDE) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209) were detected in these samples to clarify the pollution status in the metropolis. Instrumental analyses showed that the concentrations of ∑₈PBDEs ranged from 10.97 to 64.05 ng/g dry weight (dw), with an average value of 29.71 ng/g dw. BDE-209 was the predominant congener accounting for more than 97 % of total PBDEs, followed by BDE-47 and BDE-99. Remarkable spatial and seasonal distributions of PBDE concentrations were observed, suggesting that local sources, seasonal climates, and hydrologic conditions might be the influencing factors. Moderate correlations (r ²?=?0.28–0.51, p?<?0.05) were found between total organic carbon and PBDEs, which indicated that organic carbon content influenced the distributions of PBDEs in sediment of Shanghai at some extent. Hazard quotients revealed PBDEs posed no potential risk to benthic organisms in the study area at present.     

Levels and distributions of polybrominated diphenyl ethers,hexabromocyclododecane, and tetrabromobisphenol A in sediments from Taihu Lake,China

The concentrations and distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA) were investigated in 28 sediment samples collected from Taihu Lake, Eastern China. The results showed that all three classes of compounds were detected in 28 sediment samples but that PBDEs were the main contaminants in the study area. The total PBDE concentrations ranged from 3.77 to 347 ng/g dry weight (dw) with a mean value of 72.8 ng/g dw, whereas the concentrations ranged from 0.168 to 2.66 and from 0.012 to 1.30 ng/g dw for HBCD and TBBPA, respectively. In all of the sediment samples, BDE-209 was the predominant congener, accounting for 95.9 to 98.6 % of the total PBDEs, which indicated that commercial mixtures of deca-BDEs were the main sources of PBDE contamination. Higher concentrations of PBDEs were found in samples collected from Meiliang Bay and Gonghu Bay near the inflow river, which suggested that inflow runoff might play an important role in the PBDE levels in Taihu Lake sediments.     

Polybrominated diphenyl ethers in soils of the modern Yellow River Delta, China: occurrence, distribution and inventory

The Yellow River is the second largest river in China. In this study, the levels of polybrominated diphenyl ethers (PBDEs) in the modern Yellow River Delta (mYRD) were firstly reported. Twenty PBDE congeners in soil/sediment samples from mYRD were measured. The total PBDE concentrations ranged from non-detectable to 18 257 ng kg⁻¹ with a mean value of 836 ng kg⁻¹. BDE-209 was the dominant congener, accounting for ∼86.1-99.5% of the total PBDEs. The congener profiles of PBDEs with higher abundances of BDE-153 and BDE-183 were similar to those in sediment of the Bohai Sea, indicating that they shared similar sources. The concentrations and congener patterns varied among different regions. Higher levels of PBDEs were found in the middle area (MA), and more complicated congener compositions were also observed in the MA, whereas lower levels of PBDEs were found in the modern course (MC) and the old course (OC). Much more PBDEs were detected in the top layer (TL) soil where more congeners were also held compared to lower soil layers, implying that more PBDEs were emitted into this area in recent years/decades. Organic matter controlled the PBDE distribution in the soil. Soil in this area might be a source of BDE209 for the Bohai Sea.     

Polybrominated diphenyl ethers (PBDEs) in soils along a rural-urban-rural transect: sources, concentration gradients, and profiles

This study reports concentrations of PBDEs in surface soil samples collected along a 140 km transect across Kuwait to assess the role of urban centers as sources of persistent organic pollutants to the surrounding environment. The ΣPBDE concentrations varied by a factor of ∼250 and ranged from 289 to 80,078 pg g⁻¹ d.w. The concentrations of PBDEs in Kuwait City were significantly higher (p < 0.01) than those collected from sites outside the city supporting the hypothesis that urban centers are sources of PBDEs. The congener profiles were dominated by BDE-209, accounting for 93% of the PBDEs in the soil samples. The concentrations of all congeners (except BDE-209) were highly correlated with percent organic carbon (%OC) (p > 0.05) when the data from Kuwait City was omitted from the analysis. These findings suggest that soil concentrations outside the urban centers were close to equilibrium with the atmosphere.     

A contemporary assessment of polybrominated diphenyl ethers (PBDE) in the ambient air and soil of Azerbaijan

PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑₉PBDE concentrations in air and soil were 7.13 ± 1.66 pg m^?3 and 168 ± 57 pg g^?1, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g^?1), comprising ~ 96% of ∑₁₀PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.     

Distribution and temporal trend of polybrominated diphenyl ethers in one Shanghai municipal landfill, China

The scarcity of information on polybrominated diphenyl ethers’ (PBDEs) flow in landfill restricts the life cycle analysis of PBDEs. In this study, eight PBDE congeners (BDEs 28, 47, 99, 100, 153, 154, 183, and 209) in topsoil, vegetation leaves, leachate, and municipal aged refuse collected from Shanghai Laogang Municipal Landfill (SLML) were investigated. The present study revealed elevated PBDE concentrations in topsoil and proved PBDE leakage from SLML and vegetation uptake. BDE-209 was the predominant congener, and this could be due to massive usage of deca-BDE mixture in Shanghai. ΣPBDE concentrations in leachates treated by reed wetland and A²/O process fell in the low end of the worldwide range. ΣPBDE concentrations in aged refuse samples rose from under 50 ng/g dw in 1989 to the range of 5,150–5,718 ng/g dw in 2002. PBDE concentrations increase in aged refuse samples throughout the 1990s into the 2000s paralleled municipal solid waste output from 1991 to 2002 in Shanghai. Exponential increase in BDE-209 concentration in aged refuse suggested the increasing market demands for deca-BDE mixture after 1990 in China. Notably, the inventory of PBDEs in SLML was 28.7 MT, and the doubling time of BDE-209 in aged refuse was calculated to be 1.6 year. SLML can be considered as a source of PBDE and one main recipient of PBDE as well, receiving inputs predominantly from the PBDE-containing waste. Priority should be given to formulate regulation on PBDEs and sorting work before landfill disposal.     

Effect of sewage sludges contaminated with polybrominated diphenylethers on agricultural soils

The fate of polybrominated diphenyl ethers (PBDEs) in sewage sludge after agricultural application was analysed. This study was based on the analysis of sewage sludge and sludge amended soil samples collected during 2005. PBDE concentrations in sewage sludge ranged from 197 to 1185ng/g dry weight (dw), being deca-BDE-209 the predominant congener. PBDE levels in soils ranged between 21 and 690ng/g dw, being BDE-209 also the predominant congener in all soil samples. Sewage-sludge amendment at the research stations increased concentrations of all BDE congeners 1.2- to 45-fold, with the highest increases for BDE-209. Results obtained evidenced the cumulative effect of the sludge application rates. Moreover, high levels found at soils four years after the last sludge application indicate persistence of PBDEs in soils, including deca-BDE-209.     

Occurrence of polybrominated diphenyl ethers in soil from the central Loess Plateau, China: role of regional range atmospheric transport

Very few studies were conducted in highland and depositional areas in studying the transport and behavior of polybrominated diphenyl ethers (PBDEs). In this study, surface soils were collected from Huan County to investigate the level, profile, and potential influence of PBDEs via regional range atmospheric transport in the central part of the Loess Plateau (CLP) of China, one of the most extensive areas of loess deposition in the world. PBDEs were ubiquitous and log-normally distributed in soils from the CLP with mean concentrations of 0.91 and 0.54 ng g⁻¹ for ΣPBDEs (sum of PBDE congeners except for BDE-209) and BDE-209, respectively. BDE-209 was predominated congener (43.5%), followed by BDE-47 (15.7%), 99 (10.7%), and 153 (7.5%). Further principal component analysis on congener profiles showed that PBDEs in the CLP originated from similar source(s). Additionally, significant differences in the ratios of BDE-47 to 99 and BDE-153 to 154 were found between soil samples and commercial products, indicating that they have undergone fractionation during the process of regional range atmospheric transport. The deposition of PBDEs in the CLP could be influenced by the sources from surrounding regions. For example, Xi’an may have potential influence to the CLP based on geographical analysis and concentrations comparison of PBDEs in gaseous. Therefore, more studies are needed to clarify the atmospheric transport and fate of PBDEs in this region.     

Congener-specific accumulation and environmental risk assessment of polybrominated diphenyl ethers in diverse Korean sewage sludge types

Industrial, domestic wastewater, and livestock sludge samples were collected from 23 wastewater treatment plants in Korea and analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of Σ₁₉PBDE ranged from 4.01 to 10,400 ng/g dry weight. The average Σ₁₉PBDE concentrations in industrial, domestic wastewater, and livestock sludge were 1,560?±?3,610, 402?±?148, and 27.6?±?50.4 ng/g dry weight, respectively. The composition of PBDEs differed according to the type of sludge. Among the PBDE congeners, BDE 209 was dominant in all sludge samples. After BDE 209, relatively high levels were found for BDE 28 and 47 from industrial sludge, BDE 47 and 99 from domestic wastewater sludge, and BDE 206, 207, and 208 from livestock sludge. Using hierarchical cluster analysis, sludges were divided into three groups according to PBDE congener composition. A risk assessment of PBDEs in sludge used for soil amendment was carried out. Preliminary results indicated that the potential risk of soil exposed to PBDEs in sludge was relatively low.     

Levels, compositions, and inventory of polybrominated diphenyl ethers in sewage sludge of Guangdong Province, South China

Polybrominated diphenyl ethers (PBDEs) were measured in sewage sludge samples collected from major wastewater treatment plants in Guangdong Province, South China. Concentrations of ∑₃₉PBDE (all 39 compounds including tri- to hepta- PBDE congeners except for BDE-209) ranged from 3.6 to 428 ng/g dw with a mean value of 67.4 ng/g dw and a median value of 25.9 ng/g dw, and those of BDE-209 ranged from 9.9 to 5,010 ng/g dw (mean 1,024 ng/g dw and median 824 ng/g dw). The PBDE mixtures detected were mainly comprised of penta-, octa-, and deca-BDEs, with deca-BDE as the dominant constituent. The most abundant congeners, excluding BDE-209, were BDE-47, BDE-99, and BDE-183. Good correlations were found among the concentrations of BDE-47, BDE-99, BDE-100, BDE-138, and BDE-154 (r?>?0.8). However, poor correlations were found between the concentrations of BDE-209 and all other congeners (r?<?0.3). This fact suggests that most tri- to hepta-BDEs detected did not originate from decomposition of deca-BDE. The estimated annual emission of ∑_allPBDEs, ∑₃₉PBDEs, penta-BDE, octa-BDE, and deca-BDE to the Pearl River Delta environment (PRD), based on the sludge samples analyzed, amounts to 232, 20.2, 5.5, 1.7, and 212 kg per year, implicating sewage sludge as a significant source of PBDEs to the PRD environment.     

Bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers in wild frogs

To investigate bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers (PBDEs) in amphibians, we collected adult frogs (Rana limnocharis) from a rice field in an e-waste recycling site in China. We found that ∑PBDEs in the whole frogs and various tissues (brain, liver, testis and egg) ranged from 17.10 to 141.11 ng g⁻¹ wet weight. Various tissues exhibited a similar PBDE congener profile, which was characterized by intermediate brominated congeners (BDE-99 and BDE-153) as the largest contributors, with less lower brominated congeners (BDE-28 and BDE-47) and higher brominated congeners (BDE-209). The maternal transfer capacity of PBDEs declined with the increase in bromine numbers of PBDE congeners. We suggest that the bromine atom number (the molecular size, to some degree) might be a determining factor for the maternal transport of a PBDE congener rather than K_ow (Octanol-Water partition coefficient), which expresses a compound’s lipophilicity. ∑PBDEs concentrations in frogs decreased over time during a depuration period of 54 days when these wild frogs were brought to the lab from the e-waste recycling site. The half-life of ∑PBDEs was 35 days, with about 14 days for BDE-47, and 36 and 81 days for BDE-99 and BDE-153, respectively. The data shows that the elimination of PBDEs has no essential difference from aquatic and terrestrial species.     

Patterns and concentration levels of polybrominated diphenyl ethers (PBDEs) in placental tissue of women in Denmark

The levels and congener patterns of PBDEs were investigated in human placental samples in Denmark. The median concentrations of ∑PBDE_tri-hepta and BDE-209 in the 50 samples were 1.22 and 1.14 ng g⁻¹ lw, respectively, with the total sum ranging from 0.51 to 17.1 ng g⁻¹ lw, which is similar to previous placental studies. The PBDE content in placental tissue was dominated by BDE-209, which accounted for approximately 50% of the total amount of PBDEs. BDE-47, -99, and -153 were detected in all samples. Approximately equal amounts of BDE-47 and BDE-153 were observed in the placental tissue, which is in agreement with previous European studies of human serum. Principal Component Analysis (PCA) was performed to analyze congener patterns within and between mothers. The loading plot showed groupings of the measured PBDE variables in three groups, representative of Penta-, Octa- and Deca-BDE technical mixtures. Congeners representing the individual technical mixtures were close to orthogonal or inversely correlated, indicating variation in the congener patterns of internal exposure corresponding to the patterns of technical mixtures used in products. Visualisation of the participant objects according to body mass index (BMI), revealed inherent congener patterns (19% X-variance) showing increased frequency for participants within the highest BMI group to have elevated concentrations of BDE-209 in the placental tissue.     

Levels and body distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in freshwater fishes from the Yangtze River, China

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) were determined in muscle, liver and eggs of freshwater fishes from the lower reach of the Yangtze River, China. The present study is the first to report HBCD concentrations in the environment of China. The concentrations of PBDEs and HBCDs in muscle of freshwater fishes from the Yangtze River ranged from 18 to 1100ng/g and 12 to 330ng/g lipid weight (wt.), respectively. When compared with other regions of the world, the contamination of PBDEs in biota could be regarded as moderate, whereas contamination of HBCDs in biota was relatively high. The PBDE congener profiles in fishes of the present study were markedly different from those observed in freshwater and marine fishes from other regions of the world. In the present study, BDE-15, BDE-28 and BDE-47 were the predominant congeners in the fishes. This particular congener profile in fishes from the Yangtze River revealed that a specific commercial PBDE formulation (probably made in China) might have been used in the Yangtze River Delta region.     

Levels and congener specific profiles of PBDEs in human breast milk from China: implication on exposure sources and pathways

Fourteen PBDE congeners from mono- to deca-BDE were determined in breast milk of primiparous mothers from two locations in East China, i.e. Nanjing (n=9), an urban area, and Zhoushan (n=10), a semi rural coastal area. PBDEs were detected in all the human breast milk samples of the present study, indicating that general population in these two locations are widely exposed to these pollutants. Relatively higher concentrations of PBDEs were found in the milk of mothers from Nanjing than Zhoushan, suggesting the existence of significant sources of PBDEs in urban areas. PBDE levels in the present study were similar to those in European countries, but one or two orders of magnitude lower than in North America. Except for BDE-3, all congeners from di- to deca-BDE were detected in the samples of the present study. BDE-209, a congener considered to have less bioavailability, was detected in about 50% of the samples at concentrations higher than that of other congeners. Other higher brominated congeners, such as BDE-153, -197 and -207, were also prominent in the present study, which is different from the pattern generally observed in previous studies on human milk as well as biota samples. These results may indicate that the inhabitants of Nanjing and Zhoushan are exposed to location specific sources of PBDEs.     

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 1. Bioaccumulation and elimination kinetics of individual congeners and their debrominated metabolites

The uptake and elimination of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, then depurated over a five-month period. The results show that all of the studied PBDEs accumulate in fish tissues, including the higher brominated congener BDE-209. Several additional PBDE congeners were identified in the tissues of exposed fish, revealing PBDE transformation, mainly via debromination. The identified congeners originating from PBDE debromination include BDE-49 and BDE-202 and a series of unidentified tetra-, penta-, and hepta- BDEs. Contaminant assimilation efficiencies (AEs) were related to their hydrophobicity (log K_ow) and influenced by PBDE biotransformation. Metabolism via debromination appears to be a major degradation route of PBDEs in juvenile sole in comparison to biotransformation into hydroxylated metabolites.     

Levels and bioaccumulation of organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in fishes from the Pearl River estuary and Daya Bay, South China

Fifty fish samples were collected from the Pearl River estuary (PRE) and Daya Bay, South China and were analyzed for DDTs, HCHs, chlordanes and polybrominated biphenyl ethers (PBDEs). Except the high concentrations of DDT observed in fishes, the concentrations of HCHs, chlordanes and PBDEs were low when compared to other regions. BDE-47 was the predominant PBDE congener and the BDE-209 concentrations were relatively low, despite its high concentration in surface sediments. The absence of significant increase of DDT, HCH, chlordane and PBDE concentrations towards higher delta15N values, as well as the lack of a significant correlation (p<0.1) between log concentrations (lipid normalized) and delta15N, may indicate a weak biomagnification of these chemicals in the food webs. Good agreement was observed between their concentrations and lipid contents of the organisms. Bioconcentration was suggested to be responsible for the accumulation of OCPs and PBDEs in the lower trophic organisms in the studied subtropical waters.     

Determination of polybrominated diphenyl ethers (PBDEs) in fish samples from rivers and estuaries in Taiwan

Polybrominated diphenyl ethers (PBDEs) have been used extensively over the past two decades as flame retardants in many types of polymers, and have been found to be a class of contaminants of concern. Measurements of PBDEs in various environmental matrices from Sweden, Holland, Japan, North America, and elsewhere have been reported. We report data of PBDEs in fish samples taken from six rivers and three estuaries in Taiwan. Seven PBDE congeners were observed in all sixty samples. BDE-47 was found to be the dominant congener in all waters, and BDE-154 contributed more than BDE-99 and BDE-100. Nonetheless, BDE-154 and BDE-183 were the predominant congeners in some species studied. These results are somewhat different from those from other countries, where the pattern is typically BDE-47 > 99 >100 >154, 153, and is postulated to be due to the extensive use of octa-BDE rather than penta-BDE in Taiwan. The average concentration distribution across all samples of the sum of PBDE congeners ranged from 30.6 ng/g lipid to 281 ng/g lipid. The concentrations of PBDEs in fishes reported here are higher than those reported from European countries, but lower than those from the United States.     

Geographical distribution and accumulation features of PBDEs in human breast milk from Indonesia

The present study reports concentrations of polybrominated diphenyl ethers (PBDEs) and organochlorines (OCs) in human breast milk from Indonesia covering urban, suburban and rural areas. PBDEs were detected in all the samples of the present study with total concentrations ranging from 0.49 to 13 ng/g lipid wt. Geographical distribution showed that concentrations of PBDEs were relatively uniform (p>0.05) and the levels were in the same order as those in Japan and some European countries, but were one or two order lower than North America. When compared to OCs, the level of total PBDEs was lower. The congener pattern was in accordance with other studies on human matrices, in which BDE-47 was the most abundant congener. Variations of PBDE congeners in human breast milk were further discussed to elucidate the potential exposure source(s) and pathways.     

PBDEs in the supralittoral environment: the sandhopper Talitrus saltator (Montagu) as biomonitor?

In this study we evaluated the use of Talitrus saltator as biomonitor of polybrominated diphenyl ethers (PBDEs) contamination of the supralittoral zone of Mediterranean sandy shores, an area characterized by a strong input of contaminants but not yet investigated about the presence of these pollutants. We detected the presence of twenty PBDE congeners in amphipods and sand samples collected along the Tyrrhenian coast of central Italy. Eight congeners were detected in all samples. Among them, the BDE-209 was the most abundant in both amphipods and sand samples followed by BDE-99, BDE-153 and BDE-47 in animals, and BDE-99, BDE-47 and BDE-100 in sediment. The ΣPBDEs in amphipods was higher (on the average 2.5-5-fold) than in sand for almost the totality of congeners detected and each sampling site, suggesting the good capacity of sandhoppers to accumulate these pollutants. Moreover statistical analysis revealed significant differences in PBDE concentrations recorded in tissues of T. saltator among sampling sites. Therefore our results suggested the possible utilization of T. saltator as a biomonitor of PBDE contamination of the supralittoral zone of Mediterranean sandy shores.     

Polybrominated diphenyl ethers in blood from Korean incinerator workers and general population

This study was conducted to examine PBDE exposure in Koreans, with a special focus on incinerator workers due to their potential for occupational exposure to PBDEs. A total of 92 blood samples from 30 incinerator workers, 51 nearby residents and 11 controls were analyzed. The mean total PBDE concentration calculated from the 13 most concentrated congeners for all samples was 16.84+/-7.48 ng/g lipid, which was somewhat higher concentration than in other countries except North America and Canada. The PBDE levels and congener profiles detected in incinerator workers were not distinctly different from those found in the general population. In all groups tested, BDE-47 was dominant (mean contribution=32.5%) followed by BDE-153 (23.6%) and relatively high portions of BDE-183 (16.5%) were found. No strong trend was observed between PBDE levels and a number of key biological factors examined in this study, however, weak correlations were observed in PBDE levels measured against dietary habits, particularly in fish consumption frequency and gender. Overall, our data suggest that the occupational exposure of incinerator workers to PBDEs can be considered minor, while other lifestyle factors can have a greater contribution to PBDE exposure.