Debrominated, hydroxylated and methoxylated metabolism in maize (Zea mays L.) exposed to lesser polybrominated diphenyl ethers (PBDEs)

A hydroponic experiment was conducted to investigate the debrominated, hydroxylated and methoxylated metabolism of polybrominated diphenyl ethers (PBDEs, BDE-15, -28 and -47) in maize. A total of six debrominated metabolites (de-PBDEs), seven hydroxylated PBDEs (OH-PBDEs, including two unidentified OH-di-PBDEs and one unidentified OH-tri-PBDE) and four methoxylated PBDEs (MeO-PBDEs) were determined in the exposed plants. The metabolic products were detected in maize only after 12 h of exposure to the PBDEs. However, the concentration of each type of the metabolites (de-PBDEs, OH-PBDEs or MeO-PBDEs) decreased at the later exposure time, possibly due to further metabolism. The removal of a bromine atom or the introduction of a hydroxyl/methoxy group was easier at the ortho-positions on the biphenyl structure than at the para-positions. Concentration ratios of the total debrominated, hydroxylated or methoxylated metabolites to the parent congener (BDE-28 or -47) generally followed the order of leaves > stems ? roots, and MeO-PBDEs > de-PBDEs ? OH-PBDEs. These results suggest that metabolism occurred preferentially in leaves and stems than in roots. Less transformation and shorter elimination half-life of OH-PBDEs would contribute to the lower concentrations of OH-PBDEs than of de-PBDEs or MeO-PBDEs in maize.     

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.     

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in biosolids from municipal wastewater treatment plants in China

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) along with methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have been frequently identified as natural compounds in marine environment and also assumed as metabolites of PBDEs. In the present study, nine OH-PBDE, nine MeO-PBDE and 10 PBDE congeners were studied in the sewage sludge collected from 36 municipal wastewater treatment plants (WWTPs) in 27 cities of China. The results suggest that OH-PBDEs and PBDEs are ubiquitous in sewage sludge in China, however, methoxylated PBDEs were not detectable. Composition profiles of detected OH-PBDE congeners were different depending on the sampling location. ΣOH-PBDEs in WWTPs sludge ranged from 0.04 to 2.24 ng g^?1 dry weight (mean: 0.35 ng g^?1 dry weight). The total amount of the two most prominent congeners (6-OH-BDE-47 + 2′-OH-BDE-68) accounted for about 53.3–100% of the sum of all six identified congeners. A significant linear relationship was found between 6-OH-BDE-47 and 2′-OH-BDE-68. A distinct geographical distribution of ΣOH-PBDEs was observed with greater concentrations of OH-PBDEs at coastal areas than inland regions in China.     

Anthropogenic and naturally occurring polybrominated phenolic compounds in the blood of cetaceans stranded along Japanese coastal waters

We determined the residue levels and patterns of hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and related compounds, such as PBDEs, methoxylated PBDEs (MeO-PBDEs), and bromophenols (BPhs) in the blood of eleven cetacean species stranded along the Japanese coasts. The dominant OH- and MeO-PBDE isomers found in all cetaceans were 6OH-BDE47 and 6MeO-BDE47. Additionally, 2,4,6-triBPh was dominant isomer in all cetaceans. In contrast, specific differences in the distribution of para- and meta- OH-PBDE isomers and some BPhs (potential PBDEs metabolites) were found among the cetaceans.Residue levels of ΣMeO-PBDEs and 6OH-BDE47 + 2′OH-BDE68, and 2,4,6-triBPh and 6OH-BDE47 + 2′OH-BDE68 showed a significant positive correlation. These results may suggest that the large percentages of OH-PBDEs, MeO-PBDEs and 2,4,6-triBPh might share common source (i.e. biosynthesis by marine organisms), or metabolic pathway in cetacean species. Significant correlations were found between the concentrations of BDE99 and 2,4,5-triBPh. This result suggested that 2,4,5-triBPh in cetaceans could be a metabolite of BDE99.     

Seasonal variations of hydroxylated and methoxylated brominated diphenyl ethers in blue mussels from the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) found at high levels in the Baltic biota are mainly natural products, but can also be formed through metabolism or abiotic oxidation of polybrominated diphenyl ethers (PBDEs). The formation of OH-PBDEs is of concern since there is growing evidence of phenolic toxicity. This study investigates seasonal variations in levels of OH-PBDEs and MeO-PBDEs, focusing on an exposed species, the blue mussel (Mytilus edulis), sampled in the Baltic Sea in May, June, August and October of 2008. Both the OH-PBDE and MeO-PBDE levels in the mussels showed seasonal variations from May to October, the highest concentration of each congener appearing in June. The seasonal variation was more marked for OH-PBDEs than in MeO-PBDEs, but all congeners showed the same trends, except 6-MeO-BDE47 and 2′-MeO-BDE68, which did not significantly decline in concentrations after June. Biotic or abiotic debromination is suggested as a possible reason for the rapid decrease in methoxylated penta- and hexa-BDE concentrations observed in blue mussels from June to August, while the tetraBDE concentrations were stable. In addition, 1,3,7/1,3,8-tribrominated dibenzo-p-dioxins showed the same seasonal variation. The seasonal variations indicates natural formation and are unlikely to be due to transformation of anthropogenic precursors. The levels of PBDEs were fairly constant over time and considerably lower than those of the OH-PBDEs and MeO-PBDEs. The timing of the peaks in concentrations suggests that filamentous macro-algae may be important sources of these compounds found in the blue mussels from this Baltic Sea location.     

Organohalogen compounds and their metabolites in the blood of Japanese amberjack (Seriola quinqueradiata) and scalloped hammerhead shark (Sphyrna lewini) from Japanese coastal waters

Information on accumulation of polychlorinated biphenyl metabolites (OH-PCBs) and hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in the blood of marine fish is limited. The present study, we determined the residue levels and patterns of PCBs, OH-PCBs, PBDEs, OH-PBDEs and methoxylated PBDEs (MeO-PBDEs) in the blood collected from scalloped hammerhead shark (Sphyrna lewini) and Japanese amberjack (Seriola quinqueradiata), species of predatory fish at Japanese coastal waters. The predominant homologues found in Japanese amberjacks were mono- and di-chlorinated OH-PCBs, and scalloped hammerhead sharks were octa-chlorinated OH-PCBs. The predominant OH-PCB isomers were lower-chlorinated OH-PCBs such as 6OH-CB2 and 2'OH-CB9 in Japanese amberjacks. This result suggests that exposure of Japanese amberjacks to lower-chlorinated OH-PCBs might be from the ambient aquatic environment. In scalloped hammerhead sharks, 4,4'diOH-CB202, 4OH-CB201 and 4OH-CB146 were the predominant isomers accounting for approximately 60% of the total OH-PCBs. The predominant MeO-PBDE isomers were 6MeO-BDE47 followed by 2'MeO-BDE68 in both species. As for OH-PBDE isomers, 6OH-BDE47 was predominant followed by 2'OH-BDE68 in Japanese amberjacks and scalloped hammerhead sharks. Residue levels of ΣMeO-PBDEs and ΣOH-PBDEs showed a significant positive correlation (p=0.029). This result suggests that MeO-PBDEs and OH-PBDEs share a common source or a metabolic pathway in fishes. Characteristic differences found in the profiles of OH-PCBs and OH-PBDEs in Japanese amberjack and scalloped hammerhead shark show the need for further studies on the differences in exposure profiles, metabolic capacities and toxic effects in fish.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Hydroxylated and methoxylated polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins in red alga and cyanobacteria living in the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are present in the ecosystem of the Baltic Sea. OH-PBDEs are known to be both natural products from marine environments and metabolites of the anthropogenic polybrominated diphenyl ethers (PBDEs), whereas, MeO-PBDEs appear to be solely natural in origin. Polybrominated dibenzo-p-dioxins (PBDDs) are by-products formed in connection with the combustion of brominated flame retardants (BFRs), but are also indicated as natural products in a red alga (Ceramium tenuicorne) and blue mussels living in the Baltic Sea. The aims of the present investigation were to quantify the OH-PBDEs and MeO-PBDEs present in C. tenuicorne; to verify the identities of PBDDs detected previously in this species of red alga and to investigate whether cyanobacteria living in this same region of the Baltic Sea contain OH-PBDEs, MeO-PBDEs and/or PBDDs. The red alga was confirmed to contain tribromodibenzo-p-dioxins (triBDDs), by accurate mass determination and additional PBDD congeners were also detected in this sample. This is the first time that PBDDs have been identified in a red alga. The SigmaOH-PBDEs and SigmaMeO-PBDEs concentrations, present in C. tenuicorne were 150 and 4.6 ng g(-1) dry weight, respectively. In the cyanobacteria 6 OH-PBDEs, 6 MeO-PBDEs and 4 PBDDs were detected by mass spectrometry (electron capture negative ionization (ECNI)). The PBDDs and OH-PBDEs and MeO-PBDEs detected in the red alga and cyanobacteria are most likely of natural origin.     

In vitro biotransformation of PBDEs by root crude enzyme extracts: Potential role of nitrate reductase (NaR) and glutathione S-transferase (GST) in their debromination

In order to investigate the enzyme transformation of PBDEs and to track the key enzymes involved in PBDE degradation in plants, in vivo exposure of plants of ryegrass, pumpkin and maize and in vitro exposure of their root crude enzyme extracts to PBDEs were conducted. Degradation of PBDEs in the root crude enzyme solutions fit well with the first order kinetics (R² = 0.52–0.97, P < 0.05), and higher PBDEs degraded faster than the lower ones. PBDEs could be transformed to lower brominated PBDEs and hydroxylated-PBDEs by the root crude enzyme extracts with debromination as the main pathway which contributed over 90% of PBDE depletion. In vitro and in vivo exposure to PBDEs produced similar responses in root enzyme activities of which the nitroreductase (NaR) and glutathione-transferase (GST) activities decreased significantly, while the peroxidase, catalase and cytochrome P-450 activities had no significant changes. Furthermore, higher enzyme concentrations of NaR and GST led to higher PBDE debromination rates, and the time-dependent activities of NaR and GST in the root crude enzyme extracts were similar to the trends of PBDE depletion. All these results suggest that NaR and GST were the key enzymes responsible for PBDE degradation. This conclusion was further confirmed by the in vitro debromination of PBDEs with the commercial pure NaR and GST.     

In vitro metabolism of hydroxylated polybrominated diphenyl ethers and their inhibitory effects on 17β-estradiol metabolism in rat liver microsomes

Purpose

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have emerged as contaminants of environmental concerns because they pose potential risks to human and animal health. The purpose of this study was to investigate the in vitro metabolism of OH-PBDEs and their potential inhibition against 17??-estradiol (E2) metabolism.

Methods

Rat liver microsomes were used as a source of P450 enzymes in an in vitro metabolism study of OH-PBDEs. Inhibition of E2 metabolism and kinetic study were performed by incubating with rat liver microsomes in the presence of OH-PBDEs.

Results

The obtained data clearly demonstrated that OH-PBDEs, especially those congeners with lower bromination, could be metabolized to bromophenol and diOH-PBDEs. The less metabolic rate of OH-PBDEs was observed with the increasing number of bromine substituents. OH-PBDEs with hydroxyl group and bromine adjacent to the ether bridge showed faster metabolic rates. In addition, the results showed non-competitive inhibition of E2 metabolism by OH-PBDEs with IC₅₀ values in the range from 13.7 to 55.2???M. The most potent OH-PBDE inhibitor was found to be 3??-OH-BDE-100. The inhibitory potencies for OH-PBDEs were significantly higher than those of parent PBDE and methoxylated metabolites, providing the evidence that PBDEs exerted estrogenic activity in part by their hydroxylated metabolites.

Conclusions

OH-PBDEs exhibited large differences in their capacity to be metabolized and to inhibit E2 metabolism in rat liver microsomes. The finding might increase our understanding of healthy risk associated with PBDEs in human and wildlife.     

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Polybrominated diphenyl ethers and their methoxylated metabolites in anchovy (<Emphasis Type="Italic">Coilia</Emphasis> sp.) from the Yangtze River Delta,China

Background, aim, and scope  

Polybrominated diphenyl ethers (PBDEs) and their metabolites are toxic to animals, and concentrations of the PBDEs metabolites can exceed those of the parent materials. But no information was available on concentrations of PBDEs metabolites in the lower Yangtze River in the region around Jiangsu Province of China, which is heavily urbanized and industrialized area. The aims of this study were to determine whether PBDEs and their methoxylated PBDEs (MeO-PBDEs) were accumulated in Coilia sp. in this area and to investigate the potential sources for these two kinds of brominated organic pollutants.     

Identification and quantification of products formed via photolysis of decabromodiphenyl ether

Background, aim, and scope  Decabromodiphenyl ether (DecaBDE) is used as an additive flame retardant in polymers. It has become a ubiquitous environmental contaminant, particularly abundant in abiotic media, such as sediments, air, and dust, and also present in wildlife and in humans. The main DecaBDE constituent, perbrominated diphenyl ether (BDE-209), is susceptible to transformations as observed in experimental work. This work is aimed at identifying and assessing the relative amounts of products formed after UV irradiation of BDE-209. Materials and methods  BDE-209, dissolved in tetrahydrofuran (THF), methanol, or combinations of methanol/water, was exposed to UV light for 100 or 200 min. Samples were analyzed by gas chromatography/mass spectrometry (electron ionization) for polybrominated diphenyl ethers (PBDEs), dibenzofurans (PBDFs), methoxylated PBDEs, and phenolic PBDE products. Results  The products formed were hexaBDEs to nonaBDEs, monoBDFs to pentaBDFs, and methoxylated tetraBDFs to pentaBDFs. The products found in the fraction containing halogenated phenols were assigned to be pentabromophenol, dihydroxytetrabromobenzene, dihydroxydibromodibenzofuran, dihydroxytribromodibenzofuran, and dihydroxytetrabromodibenzofuran. The PBDEs accounted for approximately 90% of the total amount of substances in each sample and the PBDFs for about 10%. Discussion  BDE-209 is a source of PBDEs primarily present in OctaBDEs but also to some extent in PentaBDEs, both being commercial products now banned within the EU and in several states within the USA. It is notable that OH-PBDFs have not been identified or indicated in any of the photolysis studies performed to date. Formation of OH-PBDFs, however, may occur as pure radical reactions in the atmosphere. Conclusions  Photolysis of decaBDE yields a wide span of products, from nonaBDEs to hydroxylated bromobenzenes. It is evident that irradiation of decaBDE in water and methanol yields OH-PBDFs and MeO-PBDFs, respectively. BDE-202 (2,2′,3,3′,5,5′,6,6′-octabromodiphenyl ether) is identified as a marker of BDE-209 photolysis. Recommendations and perspectives  BDE-209, the main constituent of DecaBDE, is primarily forming debrominated diphenyl ethers with higher persistence which are more bioaccumulative than the starting material when subjected to UV light. Hence, DecaBDE should be considered as a source of these PBDE congeners in the environment. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

Comparison of monometal and multimetal adsorption in Mississippi River alluvial wetland sediment: Batch and column experiments

Monometal and multimetal adsorption of selected heavy metals in a sediment from a coastal Louisiana forested swamp used for wastewater treatment was studied. Results from the batch experiments show that the maximum adsorption capacities of the metals by the sediment were in the order of Pb ≫ Hg > Cr > Cd ⩾ Cu ⩾ Zn ≫ As based on monometal adsorption isotherm, and Hg > Cr > Cu ⩾ Cd ≈ Pb ≫ As ≈ Zn based on multimetal adsorption isotherm, respectively. Batch experimental data best fit the Langmuir model rather than the Freundlich isotherms. In the column experiments, the maximum adsorption capacities of the metals were in the order of Pb ≫ Hg > Cr > Cd > Cu > Zn ≫ As in monometal conditions, and Hg ≫ Cr ≫ Pb > Cu ⩾ Zn ≈ Cd > As in multimetal conditions. The metals became more mobile in multimetal than in monometal conditions. Results from both the batch and column experiments show that competitive adsorption among metals increases the mobility of these metals. Particularly, in this study, Pb in multimetal conditions lost it adsorption capacity most significantly. In both monometal and multimetal conditions, the maximum adsorption capacity of the metals in the column experiments was higher than that in the batch experiment indicating other metal retention mechanisms rather than adsorption may be involved. Therefore, both column and batch experiments are needed for estimating retention capacities and removal efficiencies of metals in sediments.     

Brominated phenols,anisoles, and dioxins present in blue mussels from the Swedish coastline

Introduction  

Naturally occurring hydroxylated polybrominated diphenyl ethers (OH-PBDEs), their methoxylated counterparts (MeO-PBDEs), and polybrominated dibenzo-p-dioxins (PBDDs), together with their potential precursors polybrominated phenols (PBPs) and polybrominated anisoles (PBAs), were analyzed in blue mussels (Mytilus edulis) gathered along the east coast (bordering the Baltic Sea) and west coast of Sweden (bordering the North Sea). Brown algae (Dictyosiphon foenicolaceus) and cyanobacteria (Nodularia spumigena) from the Baltic Sea, considered to be among the primary producers of these compounds, were also analyzed for comparison.     

Accumulation of hydroxylated polychlorinated biphenyls (OH-PCBs) and implications for PCBs metabolic capacities in three porpoise species

The present study investigated polychlorinated biphenyls (PCBs) and hydroxylated metabolites of PCBs (OH-PCBs) in blood from three porpoise species: finless porpoises (Neophocaena phocaenoides), harbor porpoises (Phocoena phocoena), and Dall’s porpoises (Phocoenoides dalli). The porpoises were found stranded or were bycaught along the Japanese coast. Concentrations of OH-PCB were the highest in Dall’s porpoises (58 pg g⁻¹ wet wt), second highest in finless porpoises (20 pg g⁻¹ wet wt), and lowest in harbor porpoises (8.3 pg g⁻¹ wet wt). The concentrations in Dall’s porpoises were significantly higher than the concentrations in finless porpoises and harbor porpoises (p < 0.05 and p < 0.01, respectively). There was a positive correlation between PCB and OH-PCB concentrations (r = 0.67, p < 0.001), suggesting the possible concentration-dependent induction of CYP enzymes. The three porpoise species may have exceptionally low metabolic capacities compared with other marine and terrestrial mammals, because low OH-PCB/PCB concentration ratios were found, which were 0.0016 for Dall’s porpoises, 0.0013 for harbor porpoises, and 0.00058 for finless porpoises. Distinct differences in the OH-PCB congener patterns were observed for the three species, even though they are taxonomically closely related.     

Influence of water quality parameters on occurrence of polybrominated diphenyl ether in sediment and sediment to biota accumulation

Polybrominated diphenyl ether (PBDE) concentrations in sediment and fish from 12 principal rivers in Taiwan were investigated to determine their association with water quality parameters as well as the biota-sediment accumulation factor (BSAF) in fish with different living patterns. The highest PBDE concentration in sediment was found in the Bajhang River (261 ng g^?1 dry weight (d.w.)) and the lowest in the Beinan River and the Da-an River (0.17 ng g^?1 d.w.). The PBDE concentrations in fish samples ranged from 1.28 ng g^?1 d.w. (Oreochromis niloticus niloticus) in the Yanshuei River to 33.7 ng g^?1 d.w. (Varico rhinos barbatulus) in the Da-an River. We conclude that PBDEs contamination in sediment was significantly affected by NH₃–N, pH, and DO. The BSAF results showed a parabolic trend from low- to high-brominated BDEs. Fish easily accumulated the congeners BDE-47, -100, -119, -126, and -154 from sediment. The BSAF decreased in the following order: PeBDE > HxBDE > TeBDE > other BDEs. Principle component analysis showed that demersal fish have different PBDE sources than do pelagic fish. We conclude that living and feeding habits are critical factors affecting PBDE accumulation in fish.     

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.     

Bioaccumulation, depuration and biotransformation of 4,4'-dibromodiphenyl ether in crucian carp (Carassius auratus)

Polybrominated diphenyl ethers (PBDEs) are extensively used as a class of flame retardants and have become ubiquitous environmental pollutants. Significant biotransformation of some PBDEs via reductive debromination has been observed. However, little is known about the fate of lower brominated BDEs in fish. In this study, the tissue distribution, excretion, depuration and biotransformation of 4,4′-dibromodiphenyl ether (BDE 15) were investigated in crucian carp (Carassius auratus) which were exposed to spiked water solution at different concentrations for 50 d, followed by a 14-d depuration period. Bioaccumulation parameters were calculated and the results showed that BDE 15 was mainly concentrated in the gill and liver. In particular, five biotransformation products of BDE 15 in carp were identified using GC-MS/MS. Besides two debrominated metabolites, three of the metabolites were mono-OH-BDE 15, diOH-BDE 15 and bromophenol. Our results unequivocally suggested that BDE 15 oxidation did occur via the formation of hydroxylated (OH-) metabolites in crucian carp exposed in vivo. These findings will be useful for determination of the metabolic pathways of PBDEs in freshwater fish, especially about their oxidation metabolism.