Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 2. Formation, bioaccumulation and elimination of hydroxylated metabolites

The uptake, elimination and transformation 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, and then depurated over a five-month period. Methoxylated (MeO-) and hydroxylated (OH-) PBDEs were determined in fish plasma exposed to PBDEs and compared to those obtained in control fish. While all MeO- and some OH- congeners identified in fish plasma were found to originate from non-metabolic sources, several OH- congeners, i.e., OH-tetraBDEs and OH-pentaBDEs, were found to originate from fish metabolism. Among these, 4′-OH-BDE-49 was identified as a BDE-47 metabolite. Congener 4′-OH-BDE-101, identified here for the first time, may be the result of BDE-99 metabolic transformation. Our results unequivocally showed that PBDEs are metabolised in juvenile sole via the formation of OH- metabolites. However, this was not a major biotransformation route compared to biotransformation through debromination.     

Predominance of BDE-209 and other higher brominated diphenyl ethers in eggs of white stork (Ciconia ciconia) colonies from Spain

Polybrominated diphenyl ethers (PBDEs) are ubiquitous pollutants for which there is still a lack of knowledge about the environmental behavior and fate of the higher brominated congeners (octa- to deca-BDEs). In this study, the PBDE content and congener profiles in failed eggs from two colonies of white stork (Ciconia ciconia) in Spain were studied. The average total PBDE concentration was 1.64ng/g (wet weight, w.w.) for the rural colony and 9.08ng/g (w.w.) for the urban colony. Higher brominated BDEs dominated the congener profiles of both colonies. Of particular interest was the determination of BDE-209 as the dominant congener accounting for 44.1% and 38.6% of the total PBDE content in the rural and urban colonies, respectively. BDE-202, considered an indicator of BDE 209 debromination, was detected in 83% and all of the samples from rural and urban colonies, respectively. The observed congener profile in which BDE-207>BDE-208>BDE-206 does not correspond to any known technical PBDE mixture and is evidence for possible BDE-209 degradation.     

Polybrominated diphenyl ethers and their methoxylated and hydroxylated analogs in Brown Bullhead (Ameiurus nebulosus) plasma from Lake Ontario

Polybrominated diphenyl ethers (PBDEs), methoxylated PBDEs (MeO-PBDEs) and hydroxylated PBDEs (OH-PBDEs) were detected and quantified in Brown Bullhead (Ameiurus nebulosus) from Lake Ontario. Samples were collected in 2006 from three different locations near the city of Toronto: Frenchman’s Bay, Toronto Island, and Tommy Thompson Park. A total of 117 plasma samples were pooled into 19 samples, separating males and females by site of capture. Pooled samples were analyzed for 36 PBDEs, 20 MeO-PBDEs and 20 OH-PBDEs, but only six PBDEs, five MeO- and eight OH-compounds were confirmed against standards currently available. These peaks were quantified as “identified” peaks, while peaks matching ion ratios but not matching the retention time of the available standards were quantified as “unidentified” peaks. Both “identified” and “unidentified” concentrations were combined to obtain a total concentration. No significant variations were obtained for total PBDE concentrations, ranging from 3.33 to 9.02 ng g^?1 wet weight. However, OH- and MeO-PBDE totals ranged over 1 order of magnitude among the samples (not detected – 3.57 ng g^?1 wet weight for OH-PBDEs and not detected ?0.10 ng/g wet weight for MeO-PBDE). The results of this study suggested that these compounds are ubiquitous in biota. Source estimation of MeO- and OH-PBDEs in freshwater fish were discussed. Considering that up to date no freshwater sources for MeO- or OH-PBDEs have been reported, concentrations found should be mainly related to bioaccumulation from anthropogenic sources, although other sources could not be dismissed.     

Occurrence of triclosan in plasma of wild Atlantic bottlenose dolphins (Tursiops truncatus) and in their environment

The presence of triclosan, a widely-used antibacterial chemical, is currently unknown in higher trophic-level species such as marine mammals. Blood plasma collected from wild bottlenose dolphins (Tursiops truncatus) in Charleston, SC (CHS) (n = 13) and Indian River Lagoon, FL (IRL) (n = 13) in 2005 was analyzed for triclosan. Plasma concentrations in CHS dolphins ranged from 0.12 to 0.27 ng/g wet weight (mean 0.18 ng/g), with 31% of the sampled individuals having detectable triclosan. The mean IRL dolphin plasma concentrations were 0.072 ng/g wet weight (range 0.025–0.11 ng/g); 23% of the samples having detectable triclosan. In the CHS area, triclosan effluent values from two WWTP were both 190 ng/L and primary influents were 2800 ng/L and 3400 ng/L. Triclosan values in CHS estuarine surface water samples averaged 7.5 ng/L (n = 18) ranging from 4.9 to 14 ng/L. This is the first study to report bioaccumulation of anthropogenic triclosan in a marine mammal highlighting the need for further monitoring and assessment.     

Dechlorane plus and possible degradation products in white stork eggs from Spain

The occurrence of the emerging chlorinated flame retardant Dechlorane Plus (DP) and three of its possible degradation products was investigated in white stork eggs from two colonies in Spain. The average DP concentrations were 401 pg/g wet weight (w.w.) for the urban/industrial colony and 105 pg/g w.w. for the rural colony. One possible degradation product, anti-[DP-1Cl], was found in approximately 10% of the samples. No significant stereoisomer enrichments were detected in any colony based on the average anti-DP fractional abundances found which agrees with previous studies in herring gulls. The relationship between DP and PBDE contents in both colonies was explored leading to different scenarios, i.e. no correlation was found in the urban colony but they were statistically correlated in the rural colony. To the best of our knowledge, this is the first study to report DP in a species from a terrestrial food web, and also to report a DP degradation product in biota.     

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent, effluent,receiving water,and sediment of wastewater treatment plants in Canada

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography – mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282–6.69 μg L⁻¹, 7.75–135 μg L⁻¹, and 1.53–26.9 μg L⁻¹, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009–0.045 μg L⁻¹, <0.027–1.56 μg L⁻¹, and <0.022–0.093 μg L⁻¹, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009–0.023 μg L⁻¹, <0.027–1.48 μg L⁻¹, and <0.022–0.151 μg L⁻¹ for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003–0.049 μg g⁻¹ dw, 0.011–5.84 μg g⁻¹ dw, and 0.004–0.371 μg g⁻¹ dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008–0.017 μg g⁻¹ dw, <0.007–0.221 μg g⁻¹ dw, and <0.009–0.711 μg g⁻¹ dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.     

Occurrence of co-planar polybrominated/chlorinated biphenyls (PXBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk of women from Spain

In this study, for the first time, levels and accumulation profiles of eight currently available polybrominated/chlorinated biphenyl congeners (PXBs; XB-77, -105, -118, -126A, -126B, -126C, -156 and -169, named according to IUPAC nomenclature) in human breast milk collected form Spanish women in 2005 were reported. Concentrations and congener specific profiles of polychlorinated biphenyls (PCBs), including co-planar PCBs, (co-PCBs) and polybrominated diphenyl ethers (PBDEs) were also reported.A concentration of 0.45 pg g⁻¹ lipid weight was found for total PXBs, and arithmetic mean concentrations of 125, 25 and 5.5 ng g⁻¹ lipid weight were determined for total PCBs, co-PCBs and total PBDEs respectively. Detectable levels of all congeners investigated, except CB-123 and XB-169 were found. Levels of PCBs were similar to those found in Spanish samples collected after 2000, and lower than those obtained before 2000. CB-138, -153 and -180 were the predominant PCB congeners. PBDE levels, dominated by BDE-47, -99, -100 and -209, were lower than PCB levels. PXB concentrations were the lowest, with XB-156 being the most abundant. The concentration levels of PCBs and PBDEs found in this study were in the same range as those from other European countries. Levels of PXBs were much lower than published values determined in Japan which were the only data found in the literature.