Le-Huan Yu

Bioaccumulation of several brominated flame retardants and dechlorane plus in waterbirds from an e-waste recycling region in South China: associated with trophic level and diet sources.

The present study is primarily designed to examine the role played by dietary sources on polybrominated diphenyl ethers (PBDE) congener profiles in waterbirds collected in an e-waste recycling region in South China. Some emerging halogenated flame retardants (HFRs), such as dechlorane plus (DP), 2,3,4,5,6-pentabromoethyl benzene (PBEB), pentabromotoluene (PBT), and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), were also quantified. Stable isotopes (δ(15)N and δ(13)C) were analyzed to assess the trophic levels and dietary sources of the birds. PBDEs were found to be the predominant HFRs, followed by DP, PBT, PBEB, and BTBPE. The birds in which BDE209 was predominant have differential δ(13)C and δ(15)N signatures compared with other birds, suggesting that dietary source is one of the important factors in determining the PBDE congener profile in birds. The levels of ΣPBDEs, PBEB, and PBT were significantly correlated with the trophic level (δ(15)N) for avian species which are located in a food chain, indicating the biomagnification potential of these compounds. No correlation was found between DP concentrations and trophic level of the birds. There is a significantly negative correlation between the fraction of anti-DP and δ(15)N, suggesting that the metabolic capability of DP in birds increases with the trophic level of the birds.

Tetrabromobisphenol-A and hexabromocyclododecane in birds from an e-waste region in South China: influence of diet on diastereoisomer- and enantiomer-specific distribution and trophodynamics.

Tetrabromobisphenol-A (TBBPA) and three diastereomers of hexabromocyclododecane (HBCD) were examined in the muscles of six bird species and their diet collected from an e-waste recycling region (Qingyuan) in South China. Stable isotope ratios (delta15N and delta13C) were analyzed to measure the diet source and trophic levels (TLs) of the birds. The median TBBPA and HBCD concentrations in the birds ranged from 28 to 173 and not detectable to 1995 ng/g lipid weight, respectively. The diastereoisomeric pattern shows the predominance of alpha-HBCD in birds feeding in an aquatic environment and that of gamma-HBCD in birds feeding in a terrestrial environment, whereas no clear preference for alpha isomer or gamma isomer was found in birds that inhabited freshwater wetland. A significant positive correlation between delta13C and percentage of alpha-HBCD was observed, indicating the importance of diet exposure pathways in the determination of HBCD diastereoisomer pattern. The enantiomer fractions (EFs) for alpha-HBCD differed substantially between aquatic and terrestrial bird species with a significant enrichment of (+) alpha-HBCD enantiomer for aquatic birds and a preferential enrichment of (-) alpha-HBCD enantiomer for terrestrial birds. The similarity in diastereoisomer profiles of HBCD and the EFs of alpha-HBCD between prey (fish) and predator (Chinese pond heron) also suggested that dietary exposure is an important contributor for the observed diastereoisomer- and enantiomer-specific distribution of HBCD in birds. Trophic magnification was observed for alpha-HBCD and TBBPA as concentrations increased with the TLs of the birds defined by delta15N, but only alpha-HBCD showed a strong positive relationship (p=0.001). The biomagnification factors for alpha- and gamma-HBCD and TBBPA were calculated based on individual predator/prey feeding relationships for two species.

Diasteroisomer and enantiomer-specific profiles of hexabromocyclododecane and tetrabromobisphenol A in an aquatic environment in a highly industrialized area, South China: Vertical profile, phase partition, and bioaccumulation

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) were determined in water, sediments, sediment cores, and three fish species from a river running through a highly industrialized area in South China. TBBPA concentrations exceeded those of HBCDs in the sediment and the dissolved phase of water and its levels in fish were at the high end of worldwide figures. 26% of HBCDs and 99% of TBBPA were found in dissolved phase of water. Plecostomus occupying high trophic level exhibited higher HBCD levels and higher abundance of α-HBCD than mud carp and nile tilapia which occupy low trophic level. An enrichment of (+)-α-HBCD in three fish species but (-)-α-HBCD in sediment was observed. As for γ-HBCD, most of sediment exhibited racemic while a species-dependence in fish sample was found. No clear trend was found for vertical distribution of enantiomeric profile for γ-HBCD, suggesting that the enantioselectivity of degradation of γ-HBCD is limited.

Biomagnification of Higher Brominated PBDE Congeners in an Urban Terrestrial Food Web in North China Based on Field Observation of Prey Deliveries

As an important group of brominated flame retardants, polybrominated diphenyl ethers (PBDEs) persist in the wildlife food webs. However, the biomagnification of PBDEs has not been adequately studied in the terrestrial food webs. In this study, a terrestrial food web composed of common kestrels, sparrows, rats, grasshoppers, and dragonflies in the urban environment from northern China was obtained. A field prey delivery study, reinforced by δ¹³C and δ¹⁵N analyses, indicates that sparrows are the primary prey items of common kestrels. Concentrations of PBDEs were in the following order: common kestrel > sparrow > rat > grasshopper and dragonfly with BDE-209 as the dominant congener. Biomagnification factors (BMFs) were calculated as the ratio between the lipid normalized concentrations in the predator and prey. The highest BMF (6.9) was determined for BDE-153 in sparrow/common kestrel food chain. Other higher brominated congeners, such as BDE-202, -203, -154, -183, -197, and -209, were also biomagnified in this terrestrial food chain with BMF of 1.3-4.7. BDE-47, -99, and -100 were found to be biodiluted from sparrow to common kestrel (BMFs < 1). Measured BMF values for BDE-153, -47, -99, and -100 were consistent with predicted values from a nonsteady-state model in American kestrels from another study. Retention factors and metabolism of BDE congeners may be confounding factors influencing the measured BMFs in this current study.

A review of polybrominated diphenyl ethers and alternative brominated flame retardants in wildlife from China: levels, trends, and bioaccumulation characteristics.

Accelerated industrialization and urbanization, and unregulated disposal of waste of electric and electronic equipment (e-waste) in China have caused environmental pollution of brominated flame retardants (BFRs). This review summarized the levels, trends, and bioaccumulation characteristics of polybrominated diphenyl ethers (PBDEs) and other potential alternative BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-dibromophenoxy) ethane (BTBPE) and decabromodiphenylethane (DBDPE) in wildlife from China. PBDE levels in wildlife from China were generally higher than those from other parts in Asia, and were comparable to those from Europe but were lower than those from North America. However, wildlife from the e-waste recycling sites in South China and East China contained much higher PBDEs compared to other reports around the world, suggesting the heavy contamination of PBDEs in these regions. The alternative BFRs were also detected in wildlife, revealing that the animals are exposed to these chemicals, in addition to PBDEs. Temporal trends indicated by levels in marine mammals from South China suggested that PBDE levels increased from the beginning of 1990s to 2000s, but decreased from the middle of 2000s, followed by relatively steady levels. In contrast, HBCDs were found to be continuously increasing from 1997 to 2007, indicating the increasing usage of HBCDs in China in recent years. Compared to PBDE profiles found in other parts, aquatic species and birds from China contained relatively higher contributions of BDE-28 and 209, respectively, suggesting the possible different usage pattern of PBDEs. Future works including keeping monitoring at a reasonable scale and frequency to make sure levels near urban centers indicative of population do not increase are needed. Additionally, focus effort on e-waste recycling regions to look for impacts and to determine if regulation/controls are resulting in lower environmental contamination, and incorporation of sentinel species in monitoring efforts are recommended.

Gastrointestinal absorption, metabolic debromination, and hydroxylation of three commercial polybrominated diphenyl ether mixtures by common carp

The gastrointestinal absorption, metabolic debromination, and hydroxylation of three commercial brominated diphenyl ether (BDE) mixtures were separately studied in juvenile common carp. The absorption rate of penta-BDE was higher than that of octa- and deca-BDE, likely because of the lower molecular volumes of its major congeners. However, no significantly positive relationships were found between the number of bromine atoms and the absorption rate, especially for congeners with a bromine atom number larger than six. The major congeners in fish carcass were, respectively, BDE-47 and BDE-100 in the penta-BDE exposure; BDE-154, -155, -149, and BDE-153 in the octa-BDE exposure; and BDE-154, -155, -149, -188, -179, and BDE-202 in the deca-BDE exposure. Congeners with at least one meta- or para- doubly flanked bromine atom easily undergo metabolic debromination in fish. None of the targeted MeO-polybrominated diphenyl ether (PBDE) congeners were detected in serum samples, implying that the methylation of OH-PBDE is not likely occurring in fish. Eleven OH-PBDEs and several unidentified OH-PBDE congeners were found in penta-BDE-exposed fish. The similar level among three mono-OH-BDE47 congeners suggested that the position of OH in the phenyl ring is not selective. The hydroxylation is not a significant metabolic pathway compared with debromination. No OH-PBDE congeners were found in the serum samples from deca-BDE-exposed fish, which may attributable to the low level of PBDE precursors in fish.

Accumulation pattern of Dechlorane Plus and associated biological effects on rats after 90 d of exposure

Recent studies have indicated that Dechlorane Plus (DP) is widespread in the environments. However, different isomer-specific enrichment pattern of syn-DP and anti-DP was reported in biological samples from the field. In this study, Sprague-Dawley rats were consecutively exposed to commercial DP 25 by gavage for 90 d at different doses (0, 1, 10, and 100 mg kg(-1) d(-1)) to investigate the accumulation pattern of syn-DP and anti-DP in liver, muscle, and serum of rats. The possible biological effects of DP on rats were also examined. Results showed that DP preferentially accumulated in the liver rather than in muscle at all exposure levels. No significant stereoselectivity of anti-DP or syn-DP in tissues was observed in the low DP exposure groups (0 and 1 mg kg(-1) d(-1)) with f(anti) values (defined as the concentration of the anti-DP divided by the sum of concentrations of anti- and syn-DP) ranging from 0.74 to 0.78. However, f(anti) values reduced (f(anti) ranged from 0.26 to 0.30) significantly in the high DP exposure groups (10 and 100 mg kg(-1) d(-1)) and syn-DP was predominant in all tissues. Biochemical parameters in serum, the mRNA expression levels of certain enzymes and their activities in liver were detected. There was no observable-effect in histopathology and death during the experiment, although the mRNA expression levels of some genes in the low dosage group decreased significantly and enzyme activity of CYP 2B2 increased.

Dechlorane Plus in serum from e-waste recycling workers: Influence of gender and potential isomer-specific metabolism

Dechlorane Plus (DP) and its dechlorinated product, anti-Cl₁₁-DP, were measured in serum of 70 occupationally exposed workers in an e-waste recycling region and 13 residents of an urban area in South China. The DP levels were significantly higher in the workers (22-2200 ng/g with median of 150 ng/g lipid) than in the urban residents (2.7-91 ng/g with median of 4.6 ng/g lipid). The DP concentrations in females were found to be associated with their age but such relation was not found for males. Significant differences in DP levels and DP isomer composition were found between genders. The females had remarkably higher DP levels and f(anti) values (fraction of anti-DP to total DPs) in serum than the males. Anti-Cl₁₁-DP was significantly correlated with anti-DP for both genders but with different slope of regression line. The ratios of anti-Cl₁₁-DP to anti-DP (mean of 0.017) in males were significantly higher than those (mean of 0.010) in females. Combining with the lower f(anti) values in males, it is likely that males have higher metabolic potential for DPs than females which resulted in the lower DP loading in serum. However, the different patterns of selective uptake and/or excretion of different compounds between genders cannot be eliminated as a possible reason for the observed gender differences. This study is the first to report on the gender difference in DP accumulation in human, and its mechanism is worth further investigation.

Using Compound-Specific Stable Carbon Isotope Analysis to Trace Metabolism and Trophic Transfer of PCBs and PBDEs in Fish from an e‑Waste Site, South China

Two fish species (mud carp and northern snakehead) forming a predator/prey relationship and sediment samples were collected from a pond contaminated by e-waste. The concentrations and stable carbon isotope ratios (δ(13)C) of individual polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) congeners were measured to determine if compound-specific carbon isotope analysis (CSIA) could be used to provide insight into the metabolism and trophic dynamics of PCBs and PBDEs. Significant correlations were found in the isotopic data of PCB congeners between the sediment and the fish species and between the two fish indicating identical origin of PCBs in sediment and fish. Most PCB congeners in the fish species were enriched in (13)C compared with the PCB congeners in the sediments as a result of isotopic fractionation during the metabolism of PCBs in fish. The isotopic data of several PCB congeners showing isotopic agreement or isotopic depletion could be used for source apportionment or to trace the reductive dechlorination process of PCBs in the environment. The PCB isotopic data covaried more in the northern snakehead than in the mud carp when compared to the sediment, implying that a similar isotopic fractionation occurs from the prey to the predator fish for a PCB congener possibly due to similar metabolic pathways. The PBDE congener patterns differed in the three sample types with a high abundance of BDE209, 183, 99, and 47 in the sediment, BDE47, 153, and 49 in the mud carp and BDE47, 100, and 154 in the northern snakehead. The isotopic change of BDE congeners, such as BDE47 and BDE49, in two fish species, provides evidence for biotransformation of PBDEs in biota. The results of this study suggest that CSIA is a promising tool for deciphering the fate of PCBs and PBDEs in the environment.

Polychlorinated Biphenyls (PCBs) in Human Hair and Serum from E-Waste Recycling Workers in Southern China: Concentrations, Chiral Signatures, Correlations, and Source Identification

Hair is increasingly used as a biomarker for human exposure to persistent organic pollutants (POPs). However, the internal and external sources of hair POPs remain a controversial issue. This study analyzed polychlorinated biphenyls (PCBs) in human hair and serum from electronic waste recycling workers. The median concentrations were 894 ng/g and 2868 ng/g lipid in hair and serum, respectively. The PCB concentrations in male and female serum were similar, while concentrations in male hair were significantly lower than in female hair. Significant correlations between the hair and serum PCB levels and congener profiles suggest that air is the predominant PCB source in hair and that hair and blood PCB levels are largely dependent on recent accumulation. The PCB95, 132, and 183 chiral signatures in serum were significantly nonracemic, with mean enantiomer fractions (EFs) of 0.440-0.693. Nevertheless, the hair EFs were essentially racemic (mean EFs = 0.495-0.503). Source apportionment using the Chemical Mass Balance model also indicated primary external PCB sources in human hair from the study area. Air, blood, and indoor dust are responsible for, on average, 64.2%, 27.2%, and 8.79% of the hair PCBs, respectively. This study evidenced that hair is a reliable matrix for monitoring human POP exposure.