Methoxylated Polybrominated Diphenyl Ethers Research Articles

Microplastics ingestion and endocrine disrupting chemicals (EDCs) by breeding seabirds in the east tropical Atlantic: Associations with trophic and foraging proxies (δ15N and δ13C)

In this study we found that endocrine disrupting chemicals (EDCs) were omnipresent in a tropical seabird community comprising diverse ecological guilds and distinct foraging and trophic preferences. Because EDCs tend to bioaccumulate within the food web and microplastics can absorb and release harmful chemical compounds, our findings draw attention to the potential threats to wildlife. Thus, the goal of this study was to investigate the role of plastic ingestion, trophic and foraging patterns (δ15N and δ13C) of five tropical seabird species breeding in sympatry, on the exposure to EDCs, namely Polybrominated diphenyl ethers (PBDEs), methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and personal care products (PCPs, e.g., musk fragrances and UV-filters). Results indicated that microplastics occurrence and EDCs detection frequency varied among species. Microplastics occurrence was higher in species with dual and coastal foraging strategies. Preen oil had higher levels of MeO-PBDEs and PCPs, while serum had higher levels of PBDEs. In brown boobies, the correlation between microplastics and ∑PBDEs levels was significant, suggesting that microplastics ingestion is a key PBDEs route. Trophic position (δ15N) plays a key role in PBDEs accumulation, particularly in Bulwer's petrel, which occupies a high trophic position and had more specialized feeding ecology than the other species. MeO-PBDEs were linked to foraging habitat (δ13C), although the link to foraging locations deserves further investigation. Overall, our findings not only fill key gaps in our understanding of seabirds' exposure to microplastics and EDCs, but also provide an essential baseline for future research and monitoring efforts. These findings have broader implications for the marine wildlife conservation and pollution management in sensitive environments, such as the tropical regions off West Africa.

An additional threat to populations predicted to collapse: Organobromine compounds of natural and anthropogenic sources in rough-toothed dolphins from the Southwestern Atlantic Ocean

Organic contaminants with toxic effects, like the conventional brominated flame retardants (BFRs) and BFRs of emergent concern, and their synergistic effects with other micropollutants, can be an additional threat to delphinids. Rough-toothed dolphins (Steno bredanensis) populations strongly associated with coastal environments already face a potential risk of decline due to high exposure to organochlorine pollutants. Moreover, natural organobromine compounds are important indicators of the environment's health. Polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB) and the methoxylated PBDEs (MeO-BDEs) were determined in the blubber of rough-toothed dolphins from three ecological populations from the Southwestern Atlantic Ocean (Southeastern, Southern and Outer Continental Shelf/Southern populations, SE, S, and OCS/S, respectively). The profile was dominated by the naturally produced MeO-BDEs (mainly 2′-MeO-BDE 68 and 6-MeO-BDE 47), followed by the anthropogenic BFRs PBDEs (mainly BDE 47). Median ΣMeO-BDE concentrations varied between 705.4 and 3346.0 ng g−1 lw among populations and ΣPBDE from 89.4 until 538.0 ng g−1 lw. Concentrations of anthropogenic organobromine compounds (ΣPBDE, BDE 99 and BDE 100) were higher in SE population than in OCS/S, indicating a coast – ocean gradient of contamination. Negative correlations were found between the concentration of the natural compounds and age, suggesting their metabolization and/or biodilution and maternal transference. Conversely, positive correlations were found between the concentrations of BDE 153 and BDE 154 and age, indicating low biotransformation capability of these heavy congeners. The levels of PBDEs found are concerning, particularly for SE population, because they are similar to concentrations known for the onset of endocrine disruption in other marine mammals and may be an additional threat to a population in a hotspot for chemical pollution.

A Review of Hydroxylated and Methoxylated Brominated Diphenyl Ethers in Marine Environments.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are present in the marine environment worldwide. Both OH-PBDEs and MeO-PBDEs are known natural products, whereas OH-PBDEs may also be metabolites of PBDEs. There is growing concern regarding OH-PBDEs as these compounds seem to be biological active than PBDEs. In the present study, we reviewed the available data on the contamination of OH/MeO-PBDEs in the marine environment worldwide, including seawater, marine sediment, marine plants, invertebrates, fish, seabirds and mammals. Bioaccumulation and biomagnification of OH/MeO-PBDEs in the marine food web were summarized as well. This study also proposes the future research of OH/MeO-PBDEs, including the production and the synthesis pathway of OH/MeO-PBDEs, the toxicokinetics of OH/MeO-PBDEs and the toxicology and human exposure risk assessment.

Exploring the toxic effects and mechanism of methoxylated polybrominated diphenyl ethers (MeO-PBDEs) on thyroxine-binding globulin (TBG): Synergy between spectroscopic and computations.

The interaction mechanism between thyroxine-binding globulin (TBG) and three methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was analyzed by steady-state fluorescence, ultraviolet-visible (UV-visible) spectroscopy, circular dichroism (CD), molecular docking and molecular dynamics simulation methods. The results of the molecular docking technique revealed that 2'-MeO-BDE-3, 5-MeO-BDE-47, and 3-MeO-BDE-100 combined with TBG at the active site. The steady-state fluorescence spectra displayed that MeO-PBDEs quenched the endogenous fluorescence of TBG through static quenching mechanism, and complex formation between MeO-PBDEs and TBG was further indicated by UV-vis spectroscopy. The thermodynamic quantities showed that the binding process is spontaneous, and the major forces responsible for the binding are hydrogen bonding and hydrophobic interactions, which are consistent with the results of molecular docking to a certain extent. The results of CD confirmed that the secondary structure of TBG was changed after combining with MeO-PBDEs. The dynamic simulation results illustrated that the protein structure is more compact and changes in the secondary structure of TBG after binding to MeO-PBDEs. Additionally, we also utilized the molecular mechanics/Poisson-Boltzmann surface area (MM-PBSA) method to analyze the binding free energy of TBG and MeO-PBDEs. The results suggest that van der Waals force plays an essential role in the combination.

Accumulation of PBDEs and MeO-PBDEs in notothenioid fish from the South Shetland Islands, Antarctica: An interspecies comparative study

Concentrations of polybrominated diphenyl ethers (PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs); are reported in specimens of fish notothenioids Chaenocephalus aceratus (SSI), Trematomus bernacchii (ERN), and Nototheniops nudifrons (NOD) from the South Shetland Islands, Antarctica. Significant differences in the accumulation of 2′-MeO-BDE-68 and 6-MeO-BDE-47 were detected among the analysed species. MeO-BDEs were significantly higher in SSI (11.7, 8.6, and 14.1 ng g−1 lw) than in NOD (1.63, 1.63, and 3.0 ng g−1 lw) in muscle, liver, and gill, respectively. Feeding ecology traits explain the accumulation patterns of MeO-PBDEs. SSI has a higher feeding activity with a broader diet, followed by ERN, whereas NOD is a benthic/sedentary fish with a narrower diet. The accumulation of PBDEs was neither species-, nor tissue-specific. The current study expands the knowledge concerning the accumulation of PBDEs and MeO-PBDEs in Antarctic marine fish and supports the importance of species-specificity in the accumulation of MeO-PBDEs.

Anthropogenic and natural organohalogen compounds in melon-headed whales (Peponocephala electra) stranded along the Japanese coastal waters: Temporal trend analysis using archived samples in the environmental specimen bank (es-BANK)

The present study determined recent accumulation levels of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), polychlorinated diphenyl ethers (PCDEs), methoxylated-PBDEs (MeO-PBDEs) and 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1) in the blubber of melon-headed whales (Peponocephala electra) stranded along the Japanese coastal waters in 2015 and examined temporal trends of these organohalogen compound (OHC) levels by analyzing blubber samples of this species archived in the environmental specimen bank which were collected in 1982, 2001, 2002, 2006, 2010 and 2011. The median concentrations in melon-headed whales stranded recently were in the order of DDTs ≈ PCBs > HBCDDs > Q1 > CHLs > MeO-PBDEs > PBDEs > HCB > HCHs > PCDEs, indicating that considerable amounts of HBCDDs, in addition to DDTs and PCBs, have been transported to tropical and subtropical waters of the open ocean and pelagic whale species might be exposed to relatively high levels of these OHCs. Temporal trend analyses of OHC levels in the blubber of melon-headed whales revealed significant decrease for anthropogenic OCs such as DDTs, PCBs, HCB, HCHs and PCDEs, and significant increase for CHLs, PBDEs, HBCDDs, MeO-PBDEs and Q1 since 1982. Besides, the analyses from 2001 to 2015 showed no decreasing trends (unchanged) for some PCB congeners, p,p’-DDE, cis- and trans-nonachlors, Q1, BDE-47, -100 and −154, and significantly increasing trends for α-HBCDD and 6MeO-BDE47, suggesting their chronic exposure for this pelagic whale species.

Molecular dynamics and spectral analysis for the binding of methoxylated polybrominated diphenyl ethers to lysozyme

The interaction between three methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and lysozyme was investigated using two complementary techniques: computational simulations and multi-spectroscopic methods. Molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) method was used to determine the relative binding energies. Molecular modeling analysis showed van der Waals and hydrogen bonding forces as the major forces responsible for interactions between compounds and Lysozymes. The binding site for 2′-MeO-BDE-3 and 5-MeO-BDE-47 in lysozyme was determined to be at the active pocket, where these ligands bound strongly with lysozyme tryptophan (TRP) residues TRP62, TRP63 and GLU35. In the 3-MeO-BDE-100−lysozyme system, F-shaped and T-shaped interactions between ligand and TRP62 (TRP108) were present, which suggested the stability of the combination. Fluorescence lifetime measurements suggested that be interactions between MeO-PBDEs and lysozyme could be present, and the microenvironment around the TRP residues was slightly altered during the binding process. Circular dichroism (CD) spectroscopy and UV–vis absorption spectra revealed interactions between lysozyme and MeO-PBDEs, thus inducing changes in the lysozyme microenvironment and an increase in its content of α-helix structures.

Concentrations of some legacy pollutants have increased in South Australian bottlenose dolphins from 1989 to 2014

Information about pollution and its potential impact in Australian marine wildlife is scarce. To fill this knowledge gap, our study investigated concentrations of legacy pollutants as well as naturally produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in blubber, liver, kidney and muscle of Indo-Pacific bottlenose dolphins (Tursiops aduncus) from two large inverse estuaries in South Australia from 1989 to 1995 and 2009–2014. Our results show that concentrations of most pollutant classes are relatively low compared to the literature but at the higher end of the ranges reported for marine mammals in Australia. Results for some individuals exceed toxicity thresholds indicative of immunotoxicity in marine mammals. It is important to note that concentrations of some compound classes, particularly PBDEs and polychlorinated biphenyls (PCBs), increased over a time interval of 20 years thereby placing more individuals at risk in recent years. Some of the highest concentrations of persistent organic pollutants (POPs) were measured in juveniles, which may jeopardize their development and the success of future generations. These results indicate that legacy pollutants may play a role in the long-term health of T. aduncus and should be included in biomonitoring efforts.

Insight into the transplacental transport mechanism of methoxylated polybrominated diphenyl ethers using a BeWo cell monolayer model

Methoxylated polybrominated diphenyl ethers (MeO-PBDEs), a type of emerging environmental contaminants, can accumulate through the food chain and eventually enter the human body. For pregnant women, these chemicals may be transplacentally transported to their fetuses, causing early intrauterine exposure. This study was designed to explore the transport process and characteristics of MeO-PBDEs using a BeWo cell monolayer model to simulate the placental barrier effect. Concentration-dependent transplacental transport indicates that the transport of MeO-PBDEs may be dominated by passive diffusion within the studied concentration range. According to the apparent permeability coefficients, MeO-BDE congeners investigated can be classified as poorly transported compounds, with the exception of MeO-BDE28. Time-dependent transplacental transport was observed (R2 = 0.97–0.99), which showed that the intracellular accumulation of MeO-PBDEs followed pseudo-first-order kinetics process. The transport process of MeO-PBDEs in the BeWo cell assay was not found to be sensitive to the pH of 6.5–7.4. An efflux transporter, breast cancer resistance protein, may be involved in the transport process of some MeO-PBDE congeners, and influx transporters, including organic anion transporters and organic cation transporters, may also be involved in the transport process. Although the present results indicated the possible transplacental transport mechanism, more molecular biological studies should be conducted to advance the understanding of the transport mechanisms.

Halogenated flame retardants in atmospheric particles from a North African coastal city (Bizerte, Tunisia): Pollution characteristics and human exposure

In the present study, atmospheric particle samples were collected between September 2015 and February 2016 from Bizerte city (Tunisia) to investigate the occurrence, potential sources and impacts of a range of flame retardants (FRs), including hexabromocyclododecane diastereoisomers (HBCDDs), new halogenated flame retardants (NHFRs), as well as methoxylated polybrominated diphenyl ethers (MeO-BDEs). Among 19 examined compounds, 9 congeners (α-HBCDD, β-HBCDD, γ-HBCDD, HBB, DBDPE, syn-DP, anti-DP, 2′-MeO-BDE-68 and 6-MeO-BDE-47) were detected in atmospheric particles at different levels and frequencies. Overall, the average concentration of NHFRs (1.53 pg m−3) was 1.5 and 51 folds higher than that of HBCDDs (1.04 pg m−3) and MeO-BDEs (0.03 pg m−3), respectively. By comparison with other areas of the world, NHFRs and HBCDDs in Bizerte were at medium pollution level, while MeO-BDEs were at lower levels. No significant correlations were found between NHFR, HBCDD and MeO-BDE concentrations, suggesting different sources related on one hand to the biogenic origin of MeO-BDE, and on the other hand to various types and utilisations of imported NHFR- and HBCDD-containing products, as Tunisia does not manufacture FRs. DP and HBCDD diastereoisomer profiles appeared to be divergent from their commercial products, pointing out that a complex degradation or stereoselective transformation processes occurring in ambient air around Bizerte city. The estimated daily human exposure dose (DED) to particle-bound HBCDDs, NHFRs and MeO-BDEs via outdoor air inhalation was generally at low levels. Hence, this study reports for the first time the occurrence and potential impact of HBCDDs, NHFRs and MeO-BDEs in atmospheric particles from North Africa.

A density functional theory/time-dependent density functional theory study of the structure-related photochemical properties of hydroxylated polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers and metal ion effects.

Asthe derivatives and structural analogs of polybrominated diphenyl ethers (PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have attracted increasing concern. However, knowledge of the photochemical behaviors of OH-PBDEs and MeO-PBDEs in water is limited. Here, we used density functional theory and time-dependent density functional theory to examine the structure-related photochemical properties of OH-PBDEs and MeO-PBDEs in water and the effects of metal ions as environmental factors. Eight 6-OH-PBDEs with 1-8 bromine substituents and eight 6-MeO-PBDEs with 1-8 bromine substituents were selected for this study. The optimized geometries of the selected congeners and their complexes with metals in the lowest excited triplet state (T1) showed that one C-Br bond moderately or significantly elongated. The elongated C-Br bond in the T1 state was shown in the ortho-position for the 6-OH-PBDE congeners and the ortho-position or the meta-position for the 6-MeO-PBDE congeners. For the selected congeners, there were significant positive linear correlations between the number of bromine atoms (NBr) and the calculated average atomic charge of bromine and maximum electronic absorbance wavelength (λmax), and a negative linear correlation between the NBr and average bond dissociation energy of C-O bonds (BDEC-O). The photoreactivities of the 6-OH-PBDEs and 6-MeO-PBDEs increased with an increase in the bromination degree with or without metal ions. The calculated average atomic charge of bromine and BDEC-O of the complexes with Mg2+/Zn2+ was higher and lower than those of the corresponding monomers, respectively, indicating that the presence of Mg2+/Zn2+ increased the photoreactivity (debromination and dissociation of C-O bond) of the selected 6-OH-PBDEs and 6-MeO-PBDEs. The effects of the coordination of Mg2+/Zn2+ may be overestimated due to their missing explicit solvation shell. These results provide vital insight into the photochemical properties of OH-PBDEs and MeO-PBDEs in water.

Occurrence of halogenated flame retardants in sediments and sea urchins (Paracentrotus lividus) from a North African Mediterranean coastal lagoon (Bizerte, Tunisia)

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as hexabromobenzenze (HBB), pentabromoetilbenzene (PBEB), decabromodiphenyl ethane (DBDPE) and halogenated norbornenes (HNs), as well as naturally produced methoxylated-PBDEs (MeO-PBDEs), were analyzed in 12 sediment and 30 urchin (Paracentrotus lividus) samples collected from Bizerte Lagoon in northern Tunisia. Levels of HFRs in the sediments ranged from nd to 51.8 ng/g dry weight (dw), while MeO-PBDEs were not detected. As regards levels in urchins, concentrations of PBDEs, HNs and MeO-PBDEs ranged from 3.67 to 56.9, 4.52 to 116 and nd to 364 ng/g lipid weight (lw), respectively. Thus, levels of naturally occurring compounds were higher than those of an anthropogenic origin. As regards HFRs, the highest contribution comes from HNs with levels ranging between 9.98 and 143 ng/g lw. HN and PBDE concentrations in sea urchin are similar or slightly lower than other reports for other species, while total MeO-PBDE concentrations are higher. The comsumption of sea urchins in Bizerte city is not a threat to public health concerning PBDE intakes.

Smoked fish products available in European markets: Human exposure to polybrominated diphenyl ethers and their metabolites

Food safety is continuously threatened by numerous contaminants including those originated from environmental pollution, such as PolyBrominated Diphenyl Ethers (PBDEs). In the present study, PBDEs and their biologically active metabolites – the methoxylated PBDEs (MeO-PBDEs) – were determined in several smoked seafood products (N = 30) acquired in the European market. The analyses were performed by an environmental-friendly method comprising a “Quick, Easy, Cheap, Effective, Rugged, and Safe” (QuEChERS)-based extraction followed by gas chromatography (tandem) mass spectrometry.At least one congener of each class of these flame retardants were detected in 80% of the samples assessed herein. Whenever above the limits of quantification, total PBDEs ranged from 0.21 to 64.49 μg kg−1, while MeO-PBDEs varied between 1.14 and 163.48 μg kg−1, on a wet weight basis. All smoked cod liver samples presented the highest degree of contamination, where a 100 g portion represented 12% of the PBDEs provisional tolerable weekly intake, as defined by the European food safety authority. Additionally, all tolerable daily intake percentages were below 0.2%, thus indicating no cause for concern for individuals exposed to PBDEs through consumption of smoked seafood products. Finally, multivariate partial least squares regression clarified the relationship between product characteristics and instrumental data, allowing to understand which variables caused greater influence on the contamination level of smoked products.

Fast and environmental-friendly methods for the determination of polybrominated diphenyl ethers and their metabolites in fish tissues and feed

Environmental-friendly, cost-effective and fast methods were developed and validated for the analysis of seven PolyBrominated Diphenyl Ethers (PBDEs) and eight methoxylated PBDEs (MeO-PBDEs) in three distinct seafood matrices (muscle, liver and plasma) and feed using a Quick, Easy, Cheap, Efficient, Rugged and Safe (QuEChERS) extraction approach for solid samples and a Dispersive Liquid-Liquid Microextraction method (DLLME) for plasma. Instrumental analyses were performed with gas chromatography coupled to triple quadrupole mass spectrometry using electron impact source (GC-EI-MS/MS) and negative ion chemical ionization (GC-NICI-MS) to assess BDE-209. Statistical validation showed recoveries for all target substances near 100% with average Relative Standard Deviation (RSD) lower than 9% and recovery standards higher than 65% (average RSD below 20%). Average calculated Method Detection Limits (MDLs) were lower than 65 pg·g−1 wet weight (WW) for muscle, 5.35 ng·g−1 WW for liver, 4.50 ng·g−1 WW for feed, and 0.60 ng·mL−1 for plasma samples. Quality assurance and quality control practices were comprehensively described. Methods scored high in an analytical Eco-scale, thus being classified as “an excellent green analysis”. Finally, real seafood samples collected in local markets and local fishermen were analyzed. Positive samples presented both PBDEs and MeO-PBDEs in safe amounts (0.28–125.80 ng·g−1 WW) for human consumption.

Halogenated and organophosphorus flame retardants in European aquaculture samples

This work monitors flame retardants in sediment, mussel and water samples from European fish farms. Polybrominated diphenyl ethers (PBDEs) were detected in 95% of the sediment and mussel samples with mean levels of 8.60±22.6ngg−1 dw in sediments and 0.07±0.18ngg−1 dw in mussels. BDE-209 was the main contributor for the sediments and BDE-47 was found in about 60% of the samples of both matrices. Pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB) were detected in 42% of the sediments, but not in mussels. Decabromodiphenyl ethane (DBDPE) was found in about 55% of the samples of both matrices. The same happened for dechloranes in mussels, but they were detected in 92% of the sediments. Syn-DP and anti-DP were always the main contributors. Methoxylated PBDEs (MeO-PBDEs) were detected in all mussels and some sediments, mainly 6-MeO-BDE-47 and 2′-MeO-BDE-68. Organophosphorus flame retardants (OPFRs) were found in all matrices with concentrations of 0.04–92.8ngg−1 dw in sediment, 0.50–102ngg−1 dw in mussel and 0.43–867ngl−1 in water. Only OPFRs were analysed in water samples as halogenated flame retardants and MeO-PBDEs are highly unlikely to be detected in water due to their physicochemical properties. Flame retardants have no application in fish farming so results should reflect the impact of human activity on the farm locations. A large majority of the most contaminated samples were collected from sampling spots that were at urban shores or in enclosed water bodies not completely open to the sea.

Implications of biological factors on accumulation of persistent organic pollutants in Antarctic notothenioid fish

In the present study, the possible associations between selected persistent organic pollutants (POPs) and biological factors were assessed in different tissues of two Antarctic notothenioid fish: Notothenia rossii (NOR) and Trematomus newnesi (TRN) collected at Potter Cove, King George Island/Isla 25 de Mayo, South Shetland Islands. Specifically, association patterns between biological factors (body size, lipid content, body condition) and POP concentrations (polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and metabolites, polybrominated diphenyl ethers (PBDEs), and hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), chlordanes (CHLs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs)), were explored by using two approaches: multivariate analyses (principal component analysis: PCA) and intraspecific correlations. Integrating results suggest that biological factors such as size, KI and tissue type seemed to be associated to selective accumulation of POPs for immature specimens of N. rossii, and KI and tissue type for mature specimens of T. newnesi. Each particular factor should be considered when choosing N. rossii or T. newnesi as sentinels for POPs pollution in Antarctic marine environments. Further, both nototheniids showed a selective accumulation pattern in their gonads of penta-chlorinated biphenyls (penta-CBs; 55.5 and 29ngg−1 lw for N. rossii and T. newnesi, respectively) and organochlorine pesticides such as DDTs (199 and 13.3ngg−1 lw, for N. rossii and T. newnesi respectively), and of polybrominated diphenyl ethers (PBDEs) in gills (97.2 and 22.1 for ngg−1 lw, for N. rossii and T. newnesi, respectively), highlighting the importance of these tissues in monitoring studies of pollution in fish. The current study expands the knowledge concerning the biological factors to be investigated when specific pollutants are monitored and supports the importance of tissue type for the selective accumulation of POPs in Antarctic fish. Additionally, a contribution to the scarce data on concentration of MeO-PBDEs in Antarctic marine organisms, particularly in the highly diverse perciform suborder Notothenioidei is provided.

Human exposure to brominated flame retardants through the consumption of fish and shellfish in Tarragona County (Catalonia, Spain)

The concentrations of 19 brominated flame retardants (BFRs) (8 polybrominated diphenyl ethers (PBDEs), 8 methoxylated PBDEs (MeO-PBDEs) and 3 emerging flame retardants) were determined in 10 species of fish and shellfish widely consumed in Tarragona County (Catalonia, Spain), by pressurized liquid extraction followed by gas chromatography coupled to tandem mass spectrometry. A higher occurrence of PBDEs was found in all the analyzed samples, while MeO-PBDEs were only detected in a few ones and the levels of emerging pollutants were relatively low. In contrast, hexabromobenzene was found in almost all samples at concentrations ranging between non detected and 0.2 ng g−1 wet weight (w.w.). Salmon, sole, hake, cod and tuna showed the highest concentrations of ΣPBDEs (>0.8 ng g−1 w.w.), while mussel was the species with the highest level of MeO-PBDEs (1.5 ng g−1 w.w.). The dietary exposure of BFRs through consumption of these 10 species of fish and shellfish by the population of Tarragona County was estimated for different subpopulations, classified according to age and gender. Furthermore, calculations were performed in upper-, middle- and lower-bound risk scenarios. According to our data, the current concentrations of BFRs in fish and shellfish suggest no significant health risks for the consumers.

Linking pollutant exposure of humpback whales breeding in the Indian Ocean to their feeding habits and feeding areas off Antarctica

Humpback whales, Megaptera novaeangliae, breeding off la Reunion Island (Indian Ocean) undergo large-scale seasonal migrations between summer feeding grounds near Antarctica and their reproductive winter grounds in the Indian Ocean. The main scope of the current study was to investigate chemical exposure of humpback whales breeding in the Indian Ocean by providing the first published data on this breeding stock concerning persistent organic pollutants (POPs), namely polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), DDT and its metabolites (DDTs), chlordane compounds (CHLs), polybrominated diphenyl ethers (PBDEs), and methoxylated PBDEs (MeO-PBDEs). Analyses of stable isotopes δ13C and δ15N in skin resulted in further insight in their feeding ecology, which was in agreement with a diet focused mainly on low trophic level prey species, such as krill from Antarctica. POPs were measured in all humpback whales in the order of HCB > DDTs > CHLs > HCHs > PCBs > PBDEs > MeO-BDEs. HCB (median: 24 ng g−1 lw) and DDTs (median: 7.7 ng g−1 lw) were the predominant compounds in all whale biopsies. Among DDT compounds, p,p′-DDE was the major organohalogenated pollutant, reflecting its long-term accumulation in humpback whales. Significantly lower concentrations of HCB and DDTs were found in females than in males (p < 0.001). Other compounds were similar between the two genders (p > 0.05). Differences in the HCB and DDTs suggested gender-specific transfer of some compounds to the offspring. POP concentrations were lower than previously reported results for humpback whales sampled near the Antarctic Peninsula, suggesting potential influence of their nutritional status and may indicate different exposures of the whales according to their feeding zones. Further investigations are required to assess exposure of southern humpback whales throughout their feeding zones.

Occurrence and trophic magnification of polybrominated diphenyl ethers (PBDEs) and their methoxylated derivatives in freshwater fish from Dianshan Lake, Shanghai, China

In this study, polybrominated diphenyl ethers (PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were analyzed in eleven freshwater fish species from Dianshan Lake, Shanghai, China. The highest concentrations of PBDEs and MeO-PBDEs were found in snakehead, with mean values of 38 ng g−1 lw and 4.2 ng g−1 lw, respectively. BDE-47 was the predominant congener of PBDEs, followed by BDE-154. Congener pattern variation of PBDEs was observed among different fish species, implying differences in biotransformation potential among fish. Yellow catfish showed highest concentrations of BDE-99, -153 and -183, suggesting that it is more resistant to debromination than any other fish analyzed in the present study. Trophic magnification factors were in the range of 1.35–1.81 for all the PBDE congeners, but not for 2′-MeO-BDE-68. Negative relationship was observed between PBDEs concentration and sample size (length and weight), indicating fish size dilution effect.

Transformation of hydroxylated and methoxylated 2,2′,4,4′,5-brominated diphenyl ether (BDE-99) in plants

The occurrence and fate of hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have received significant attention. However, there is limited information on the metabolism relationship between OH-pentaBDEs and MeO-pentaBDEs that were frequently detected with relatively high concentrations in the environment. In this study, the biotransformation between OH-BDE-99 and MeO-BDE-99 was investigated in rice, wheat, and soybean plants. All the three plants can metabolize OH-BDE-99 to corresponding homologous methoxylated metabolites, while the transformation from MeO-BDE-99 to OH-BDE-99 could only be found in soybean. The conversion of parent compounds was the highest in soybean, followed by wheat and rice. Transformation products were found mainly in the roots, with few metabolites being translocated to the shoots and solution after exposure. The results of this study provide valuable information for a better understanding of the accumulation and transformation of OH-PBDEs and MeO-PBDEs in different plants.