Partitioning of Chlorinated Paraffins (CPs) to Daphnia magna Overlaps between Restricted and in-Use Categories.

Chlorinated paraffins (CPs) are high-production volume industrial chemicals consisting of n-alkanes (with 10 to 30 carbon atoms in the chain) with chlorine content from 30 to 70% of weight. In Europe, the use of short chain chlorinated paraffins (SCCPs) has been restricted by the Stockholm Convention on POPs due to their PBT (persistent, bioaccumulative and toxic) properties. Medium (MCCPs) and long chain (LCCPs) chlorinated paraffins are used as substitution products. In this work we studied the partitioning behavior of five different CP technical mixtures from the established categories (2 SCCPs, 1 MCCP, 1 LCCP and 1 CP technical mixture covering all categories) using passive dosing, by determining the partitioning coefficient of CP technical mixtures between silicone and water ( Ksilicone-water) as well as between organic matter and water ( Koc-water). We show that both silicone-water and organic carbon-water partition coefficients overlap between different categories of CP technical mixtures. These results indicate that in-use MCCPs and LCCPs may be equally or more bioaccumulative than restricted SCCPs. For the tested mixtures, both chlorine content and carbon chain length showed a significant correlation with both Ksilicone-water and Koc-water.

Novel octabrominated phenolic diphenyl ether identified in blue mussels from the Swedish West Coast.

Hydroxylated (OH-) and methoxylated (MeO-) polybrominated diphenyl ethers (PBDEs) are compounds present in the marine environment and OH-PBDEs are of toxicological concern and are therefore of interest to monitor in the environment. A phenolic octaBDE was tentatively identified in the phenolic fraction of previously analyzed mussel samples after methylation of the halogenated phenolic compounds (HPCs). The aim of the present study was to confirm the identity of this compound in blue mussels and investigate whether the analyte is diOH- and/or OH-MeO-octaBDE. Two reference standards, 6,6'-dimethoxy-2,2',3,3',4,4',5,5'-octabromodiphenyl ether (6,6'-diMeO-BDE194) and 6-ethoxy-6'-methoxy-2,2',3,3',4,4',5,5'-octabromodiphenyl ether (6-EtO-6'-MeO-BDE194) were prepared via O-arylation of 2,3,4,5-tetrabromo-6-methoxyphenol and 2,3,4,5-tetrabromo-6-ethoxyphenol, respectively, with a novel unsymmetrical diaryliodonium salt, 2,3,4,5-tetrabromo-6-methoxydiphenyliodonium triflate. The GC retention time and GC/MS spectrum of the synthesized 6,6'-diMeO-BDE194 correspond well with the analyte in the methylated phenolic fraction of a mussel extract from a previous study. Structural analysis performed in this study indicate that the synthesized 6,6'-diMeO-BDE194 and 6-EtO-6'-MeO-BDE194 correspond well with 6-hydroxy-6'-methoxy-2,2',3,3',4,4',5,5'-octabromodiphenyl ether (6-OH-6'-MeO-BDE194) after methylation and ethylation, respectively, of the HPCs in the mussel extracts. The compound 6-OH-6'-MeO-BDE194 was identified and quantified in new mussels, sampled in 2012 from two locations on the Swedish west coast, with geometric mean concentrations of 3700 and 410 ng/g fat, respectively.

Disruption of oxidative phosphorylation (OXPHOS) by hydroxylated polybrominated diphenyl ethers (OH-PBDEs) present in the marine environment.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are of growing concern, as they have been detected in both humans and wildlife and have been shown to be toxic. Recent studies have indicated that OH-PBDEs can be more toxic than PBDEs, partly due to their ability to disrupt oxidative phosphorylation (OXPHOS), an essential process in energy metabolism. In this study, we determined the OXPHOS disruption potential of 18 OH-PBDE congeners reported in marine wildlife using two in vitro bioassays, namely the classic rat mitochondrial respiration assay, and a mitochondrial membrane potential assay using zebrafish PAC2 cells. Single OH-PBDE congeners as well as mixtures were tested to study potential additive or synergistic effects. An environmental mixture composed of seven OH-PBDE congeners mimicking the concentrations reported in Baltic blue mussels were also studied. We report that all OH-PBDEs tested were able to disrupt OXPHOS via either protonophoric uncoupling and/or inhibition of the electron transport chain. Additionally we show that OH-PBDEs tested in combinations as found in the environment have the potential to disrupt OXPHOS. Importantly, mixtures of OH-PBDEs may show very strong synergistic effects, stressing the importance of further research on the in vivo impacts of these compounds in the environment.

Metabolite alterations in zebrafish embryos exposed to hydroxylated polybrominated diphenyl ethers.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are formed by metabolism from the flame retardants polybrominated diphenyl ethers (PBDEs). In the aquatic environment, they are also produced naturally. OH-PBDEs are known for their potential to disrupt energy metabolism, the endocrine system, and the nervous system. This is the first study focusing on the effects of OH-PBDEs at the metabolite level in vivo. The aim of the current study was to investigate the metabolic effects of exposure to OH-PBDEs using metabolomics, and to identify potential biomarker(s) for energy disruption of OH-PBDEs. Zebrafish (Danio rerio) embryos were exposed to two different concentrations of 6-OH-BDE47 and 6-OH-BDE85 and a mixture of these two compounds. In total, 342 metabolites were annotated and 79 metabolites were affected in at least one exposure. Several affected metabolites, e.g. succinic acid, glutamic acid, glutamine, tyrosine, tryptophan, adenine, and several fatty acids, could be connected to known toxic mechanisms of OH-PBDEs. Several phospholipids were strongly up-regulated with up to a six-fold increase after exposure to 6-OH-BDE47, a scarcely described effect of OH-PBDEs. Based on the observed metabolic effects, a possible connection between disruption of the energy metabolism, neurotoxicity and potential immunotoxicity of OH-PBDEs was suggested. Single compound exposures to 6-OH-BDE47 and 6-OH-BDE85 showed little overlap in the affected metabolites. This shows that compounds of similar chemical structure can induce different metabolic effects, possibly relating to their different toxic mechanisms. There were inter-concentration differences in the metabolic profiles, indicating that the metabolic effects were concentration dependent. After exposure to the mixture of 6-OH-BDE47 and 6-OH-BDE85, a new metabolic profile distinct from the profiles obtained from the single compounds was observed. Succinic acid was up-regulated at the highest, but still environmentally relevant, concentration of 6-OH-BDE47, 6-OH-BDE85, and the mixture. Therefore, succinic acid is suggested as a potential biomarker for energy disruption of OH-PBDEs.

Correlating seasonal changes of naturally produced brominated compounds to biomarkers in perch from the Baltic Sea.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs), naturally produced by algae and cyanobacteria in the Baltic Sea, are potent disrupters of energy metabolism as well as endocrine disruptors and neurotoxins. In this study, European perch (Perca fluviatilis) from the Baltic Sea were sampled from May until October. OH-PBDEs and ten biomarkers were measured in each individual (n = 84 over 18 sampling time points) to study potential correlations between exposure to OH-PBDEs and changes in biomarkers. Several biomarkers showed significant non-linear seasonal variation. In the perch, ethoxyresorufin-O-deethylase (EROD) activity, plasma lactate concentration, and plasma glucose concentration showed a significant positive log-linear correlation with OH-PBDEs, whereas lipid percentage and liver somatic index showed a significant negative log-linear correlation with OH-PBDEs. These results strengthen the concern that OH-PBDEs could cause negative health effects for fish in the Baltic Sea.

Modeling relationships between Baltic Sea herring (Clupea harengus) biology and contaminant concentrations using multivariate data analysis.

Baltic Sea herring (Clupea harengus) is a pelagic, zoo-planktivorous fish and young (2-5 years old) individuals of this species are sampled annually in the Swedish marine monitoring program. This study determined concentrations of organochlorines (OCs) and brominated flame retardants (BFRs) in dorsal muscle from herring (n = 60) of varying age (2-13 years), weight (25-200 g), and body length (16-29 cm) caught at three locations in the Swedish part of the Baltic Proper. In order to ensure that the fish biology was as varied as possible, though still similar from all sampling sites, the fish to be chemically analyzed were selected from a large number of fish with determined biology using Multivariate Design. In statistical evaluation of the data, univariate and multivariate data analysis techniques, e.g. principal components analysis (PCA), partial least-squares regression (PLS), and orthogonal PLS (OPLS), were used. The results showed that the fish are exposed to a cocktail of contaminants and levels are presented. Significant OPLS models were found for all biological variables versus concentrations of OCs and BFRs, showing that fish biology covaries with fish contaminant concentrations. Correlation coefficients were as high as 0.98 for e.g. ßHCH concentration (wet weight) versus the lipid content. Lastly, the OC concentrations in herring muscle were modeled against the BFR concentrations to determine whether concentrations of either could be used to predict the other. It was found that OPLS models allowed BFR concentrations to be predicted from OC concentrations with high, but varying, accuracy (R(2)Ys between 0.93 to 0.75). Thus, fish biology and contaminant concentrations are interwoven, and fish biological parameters can be used to calculate (predict) contaminant concentrations. It is also possible to predict the BFR concentrations in an individual fish from its concentrations of OCs with very high accuracy.

Correction to: Chlorinated and brominated organic pollutants in shellfish from the Yellow Sea and East China Sea.

The article Chlorinated and brominated organic pollutants in shellfish from the Yellow Sea and East China Sea, written by Ge Yin, Lillemor Asplund, Yanling Qiu, Yihui Zhou, Hua Wang, Zongli Yao, Jianbin Jiang and Åke Bergman.

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.

Using raptors as environmental sentinels: monitoring the white-tailed sea eagle Haliaeetus albicilla in Sweden.

This paper summarizes results from the monitoring of reproduction of white-tailed sea eagle in Sweden 1965-2006. Since 1989 the eagle population on the Swedish Baltic coast has been included in the National Environment Monitoring Program as an indicator species for potentially harmful chemicals. The percentage of successfully reproducing pairs and nestling brood size decreased in synchrony with rising concentrations of contaminants in the 1950s on into the 1970s. Mean productivity was 1.3 young per pair prior to 1950 and decreased to 0.3 in 1965-1985. Dichlorodiphenyldichloroethene (DDE) in eagle eggs decreased from a range of annual means in 1965-1974 of 600-1200 microg g(-1) (lipid weight) to 60-140 microg g(-1) in 1996-2005. Total polychlorinated biphenyl (PCB) concentrations averaged above 1000 microg g(-1) into the early 1980s and remained in the range of 250-500 microg g(-1) in 1996-2005. Productivity began to improve when concentrations of DDE and PCBs dropped below approximately 300 and 800 microg g(-1), respectively. Brood size remains below the pre-1950 level in one coastal region, indicating a possible impact from other contaminants. The power to detect significant trends under the program is presented and discussed: if white-tailed sea eagle reproduction had been monitored earlier during the 20th century, the negative impact of dichlorodiphenyltrichloroethane (DDT, source of DDE) would have been signaled as early as the 1950s in the Baltic Sea. The dramatic fall of white-tailed sea eagle reproduction under the influence of DDT and PCBs, and the subsequent rise following their ban, illustrates the usefulness of raptors like sea eagles as sentinels for environmental pollutants.

Survey of estrogenic and androgenic disruption in Swedish coastal waters by the analysis of bile fluid from perch and biomarkers in the three-spined stickleback.

The potential for endocrine disruption close to sewage treatment plant and pulp mill effluent discharge points along the Swedish Baltic Sea coast was explored using a dual survey strategy employing two stationary fish species. The levels of vitellogenin and spiggin as biomarkers of endocrine disruption were determined in juvenile three-spined sticklebacks (Gasterosteus aculeatus L.) together with the sex ratios and the presence of intersex. As an indication of exposure, estrogenic and androgenic substances were analysed by GC-MS in bile from perch (Perca fluviatilis L.). Spiggin and vitellogenin levels in juvenile three-spined sticklebacks were generally low, and, for most sampling sites no deviation in gonad type ratios were observed. No remarkable levels of natural or synthetic estrogens or androgens were observed in bile fluid from perch, while bisphenol A and 4-nonylphenol were detected in perch from both reference sites and exposed sites. Taken together, the results did not indicate estrogenic or androgenic disruption in the investigated waters.

Biosynthesis of hydroxylated polybrominated diphenyl ethers and the correlation with photosynthetic pigments in the red alga Ceramium tenuicorne.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have been identified in a variety of marine organisms from different trophic levels indicating a large spread in the environment. There is much evidence pointing towards natural production as the major source of these compounds in nature. However, much is still not known about the natural production of these compounds. Seasonal trend studies have shown large fluctuations in the levels of OH-PBDEs in Ceramium tenuicorne from the Baltic Sea. Yet, even though indications of stimuli that can induce the production of these compounds have been observed, none, neither internal nor external, has been assigned to be responsible for the recorded fluctuations. In the present study the possible relationship between the concentration of pigments and that of OH-PBDEs in C. tenuicorne has been addressed. Significant correlations were revealed between the concentrations of all OH-PBDEs quantified and the concentrations of both chlorophyll a and Σxanthophylls + carotenoids. All of which displayed a concentration peak in mid-July. The levels of OH-PBDEs may be linked to photosynthetic activity, and hence indirectly to photosynthetic pigments, via bromoperoxidase working as a scavenger for hydrogen peroxide formed during photosynthesis. Yet the large apparent investment in producing specific OH-PBDE congeners point towards an targeted production, with a more specific function than being a waste product of photosynthesis. The OH-PBDE congener pattern observed in this study is not agreeable with some currently accepted models for the biosynthesis of these compounds, and indicates a more selective route than previously considered in C. tenuicorne.

A refined method for analysis of 4,4'-dicofol and 4,4'-dichlorobenzophenone.

The acaricide, dicofol, is a well-known pesticide and partly a substitute for dichlorodiphenyltrichloroethane (DDT). Only few reports on environmental occurrence and concentrations have been reported calling for improvements. Hence, an analytical method was further developed for dicofol and dichlorobenzophenone (DCBP) to enable assessments of their environmental occurrence. Concentrated sulfuric acid was used to remove lipids and to separate dicofol from DCBP. On-column injection was used as an alternative to splitless injection to protect dicofol from thermal decomposition. By the method presented herein, it is possible to quantify dicofol and DCBP in the same samples. Arctic cod (Gadus morhua) were spiked at two dose levels and the recoveries were determined. The mean recovery for dicofol was 65% at the low dose (1 ng) and 77% at the high dose (10 ng). The mean recovery for DCBP was 99% at the low dose (9.2 ng) and 146% at the high dose (46 ng). The method may be further improved by use of another lipid removal method, e.g., gel permeation chromatography. The method implies a step forward in dicofol environmental assessments.

Human exposure to PCDDs and their precursors from heron and tern eggs in the Yangtze River Delta indicate PCP origin.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are highly toxic to humans and wildlife. In the present study, PCDD/Fs were analyzed in the eggs of whiskered terns (Chlidonias hybrida), and genetically identified eggs from black-crowned night herons (Nycticorax nycticorax) sampled from two lakes in the Yangtze River Delta area, China. The median toxic equivalent (TEQ) of PCDD/Fs were 280 (range: 95-1500) and 400 (range: 220-1100) pg TEQ g-1 lw (WHO, 1998 for birds) in the eggs of black-crowned night heron and whiskered tern, respectively. Compared to known sources, concentrations of PCDDs relative to the sum of PCDD/Fs in bird eggs, demonstrated high abundance of octachlorodibenzo-p-dioxin (OCDD), 1,2,3,4,6,7,8-heptaCDD and 1,2,3,6,7,8-hexaCDD indicating pentachlorophenol (PCP), and/or sodium pentachlorophenolate (Na-PCP) as significant sources of the PCDD/Fs. The presence of polychlorinated diphenyl ethers (PCDEs), hydroxylated and methoxylated polychlorinated diphenyl ethers (OH- and MeO-PCDEs, known impurities in PCP products), corroborates this hypothesis. Further, significant correlations were found between the predominant congener CDE-206, 3'-OH-CDE-207, 2'-MeO-CDE-206 and OCDD, indicating a common origin. Eggs from the two lakes are sometimes used for human consumption. The WHO health-based tolerable intake of PCDD/Fs is exceeded if eggs from the two lakes are consumed regularly on a weekly basis, particularly for children. The TEQs extensively exceed maximum levels for PCDD/Fs in hen eggs and egg products according to EU legislation (2.5 pg TEQ g-1lw). The results suggest immediate action should be taken to manage the contamination, and further studies evaluating the impacts of egg consumption from wild birds in China. Likewise, studies on dioxins and other POPs in common eggs need to be initiated around China.

Gas chromatography and mass spectrometry of methoxylated polybrominated diphenyl ethers (MeO-PBDEs).

Twenty-six methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were characterized by gas chromatography (GC) on four different GC columns with different lengths and polarities, as well as by mass spectrometry using three ionization techniques, electron ionization (EI), electron capture negative ionization (ECNI) and positive ion chemical ionization (PICI). MeO-PBDE congeners with similar retention times on a nonpolar GC column were separated when analyzed on a polar GC column. EI can be used to determine the position of the methoxy substituent (ortho, meta or para) relative to the diphenyl ether oxygen in the MeO-PBDEs. The PICI ionization technique is shown to be valuable to generate structural information of the MeO-PBDEs, i.e. the degree of bromination on both the methoxy-substituted ring and the entirely brominated phenyl ring can be obtained. This structure information can also be achieved for certain MeO-PBDEs with the methoxy group in ortho position to the diphenyl ether bond in ECNI mode. Like other brominated compounds ECNI is preferable when analyzing environmental samples for quantification of MeO-PBDEs because of the formation of bromide ions, which enables low detection limits.

Fish bile used to detect estrogenic substances in treated sewage water.

Endocrine disrupting effects on fish associated with sewage treatment effluents have been demonstrated in several studies. To investigate if the effluents from two modern Swedish sewage treatment plants contained estrogenic substances, juvenile rainbow trout were exposed to sewage water before and after the last treatment step which is a sand filter. As a biomarker for estrogenic effect, vitellogenin was analysed in the blood plasma of the exposed fish. To identify substances possibly responsible for the effect, bile fluid from the exposed fish were analysed with GC/MS. Elevated levels of vitellogenin were only seen in the fish exposed at one of the sewage treatment plants, the one with shorter residence time in the biological treatment steps, which suggests that the residence time is of importance for the ability to reduce the amount of estrogenic substances in the sewage water. The highest elevation of vitellogenin was seen in the fish exposed to water before the sand filter, which indicates that the sand filter contributes to further reduction of estrogenic substances in the sewage water. In bile from the same group of fish, considerably higher concentrations of estrone, bisphenol A and 4-nonylphenol (4.0 microg/g bile, 23 microg/g bile and 24 microg/g bile, respectively) were observed compared to bile from control fish (<0.04 microg/g bile, 0.21 microg/g bile, and 3.5 microg/g bile, respectively). The more potent steroidal estrogens were suggested to be major contributors to the observed estrogenic effect, although xenoestrogens were detected at higher concentrations in the bile fluid.

Multivariate data analysis of organochlorines and brominated flame retardants in Baltic Sea guillemot (Uria aalge) egg and muscle.

Concentrations of organochlorines (OCs) and brominated flame-retardants (BFRs) were determined in guillemot (Uria aalge) eggs from the island of Stora Karlsö in the Baltic Sea where 10 eggs/year were collected in the years 2000, 2001 and 2002. The dominating contaminant in egg was p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) with a geometric mean (GM) concentration of 18200 ng/g lipid weight (lw). The GM concentration in egg of hexabromocyclododecane (HBCD) of 140 ng/glw, was significantly higher than that of polybrominated diphenyl ether (summation operatorPBDE) of 77 ng/glw. For the evaluation of the data multivariate data analysis techniques namely principal components analysis (PCA), partial least squares regression (PLS), soft independent modelling of class analogy (SIMCA classification), and PLS discriminant analysis (PLS-DA), were used. We investigated whether the eggs' biological characteristics co-varied with egg concentrations of OCs and BFRs, and found e.g., significant negative correlations between egg weight and concentrations of HCB and p,p'-DDE. A PLS model with analyzed BFRs as the Y matrix and OCs as the X matrix could, with varying accuracy, calculate the concentrations of BFRs in the individual egg from their concentrations of OCs (e.g., R(2)Y of 0.89 for BDE47, and of 0.50 for HBCD). Lastly, we compared the contaminant concentrations in the eggs to those in previously analyzed pectoral muscles from adult guillemots from Stora Karlsö, from the year 2000. A PLS-DA model, showed that some of the contaminants (e.g., HBCD and CB28) had significantly higher concentrations in egg than in muscle, although 7 of the 14 contaminants showed no difference in concentrations between the two matrices.

Spectral characterization of two bioaccumulated methoxylated polybrominated diphenyl ethers.

Two methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were isolated from a True's beaked whale (Mesoplodon mirus) and identified by NMR (1H, 1H-1H and 1H-13C) and high resolution mass spectrometry as 2-(2',4'-dibromophenoxy)-3,5-dibromoanisole (6-MeO-BDE47) and 2-(2',4'-dibromophenoxy)-4,6-dibromoanisole (2'-MeO-BDE68). Previously the structures of these bioaccumulated compounds have been determined by comparison of their mass spectra and gas chromatographic (GC) retention times with those of authentic standards. While this method is accepted and generally successful, NMR of the isolated compounds allows us to definitively identify the congeners. Our characterizations are consistent with those made for MeO-PBDEs in other organisms, identified by chromatographic methods.

Trophic transfer of naturally produced brominated aromatic compounds in a Baltic Sea food chain.

Brominated aromatic compounds (BACs) are widely distributed in the marine environment. Some of these compounds are highly toxic, such as certain hydroxylated polybrominated diphenyl ethers (OH-PBDEs). In addition to anthropogenic emissions through use of BACs as e.g. flame retardants, BACs are natural products formed by marine organisms such as algae, sponges, and cyanobacteria. Little is known of the transfer of BACs from natural producers and further up in the trophic food chain. In this study it was observed that total sum of methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and OH-PBDEs increased in concentration from the filamentous red alga Ceramium tenuicorne, via Gammarus sp. and three-spined stickleback (Gasterosteus aculeatus) to perch (Perca fluviatilis). The MeO-PBDEs, which were expected to bioaccumulate, increased in concentration accordingly up to perch, where the levels suddenly dropped dramatically. The opposite pattern was observed for OH-PBDEs, where the concentration exhibited a general trend of decline up the food web, but increased in perch, indicating metabolic demethylation of MeO-PBDEs. Debromination was also indicated to occur when progressing through the food chain resulting in high levels of tetra-brominated MeO-PBDE and OH-PBDE congeners in fish, while some penta- and hexa-brominated congeners were observed to be the dominant products in the alga. As it has been shown that OH-PBDEs are potent disruptors of oxidative phosphorylation and that mixtures of different congener may act synergistically in terms of this toxic mode of action, the high levels of OH-PBDEs detected in perch in this study warrants further investigation into potential effects of these compounds on Baltic wildlife, and monitoring of their levels.

Hydroxylated and methoxylated polybrominated diphenyl ethers in long-tailed ducks (Clangula hyemalis) and their main food, Baltic blue mussels (Mytilus trossulus × Mytilus edulis).

Long-tailed ducks (Clangula hyemalis) that breed in northern Europe and western Siberia and commonly winter in the Baltic Sea, are threatened by a significant population decrease. The ducks are, by primarily feeding on Baltic blue mussels (Mytilus trossulus × Mytilus edulis) while wintering in the Baltic Sea, potentially subjected to high levels of toxic hydroxylated polybrominated diphenyl ethers (OH-PBDEs). To assess long-tailed ducks exposure to polybrominated phenols (PBPs), polybrominated anisoles (PBAs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), their methylated counterparts (MeO-PBDEs) and polybrominated diphenyl ethers (PBDEs), livers of ten long-tailed ducks wintering in the Baltic Sea were analysed. Pattern and levels of analytes in long-tailed ducks (liver) and blue mussels sampled in March and May at nine sites in the Baltic Sea were compared. The geometric mean concentration (ng/g l.w.) in livers of long-tailed ducks and Baltic blue mussels were: Σ(2)PBPs: 0.57 and 48; Σ(2)PBAs: 0.83 and 11; Σ(7)OH-PBDEs: 6.1 and 45; Σ(7)MeO-PBDEs: 3.8 and 69; Σ(7)PBDEs: 8.0 and 7.2, respectively. Based on an estimated daily intake of 450 g fresh blue mussel meat, long-tailed ducks daily dietary intake of brominated substances while foraging in the Baltic Sea in March-May was estimated to; 390 ng Σ(2)PBPs, 90 ng Σ(2)PBAs, 370 ng Σ(7)OH-PBDEs, 590 ng Σ(7)MeO-PBDEs and 59 ng Σ(7)PBDEs. The low levels of PBPs, PBAs, OH-PBDEs and MeO-PBDEs in the long-tailed duck livers compared to blue mussel, despite a continuous daily intake, suggest that these compounds are poorly retained in long-tailed ducks.

Anthropogenic and naturally produced brominated substances in Baltic herring (Clupea harengus membras) from two sites in the Baltic Sea.

In the eutrophicated Baltic Sea, several naturally produced hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have been found in marine biota. OH-PBDEs are toxic to adult and developing zebrafish and shown to be potent disruptors of oxidative phosphorylation (OXPHOS). Disturbed OXPHOS can result in altered energy metabolism and weight loss. In herring, the concentration of OH-PBDEs (i.e. 2'-OH-BDE68 and 6-OH-BDE47) has increased during the period 1980-2010 in the Baltic Proper. Over the same time period, the condition and fat content in Baltic herring have decreased. Given the toxicity and increasing trends of OH-PBDEs in Baltic herring it is important to further assess the exposure to OH-PBDEs in Baltic herring. In this study, the concentrations of OH-PBDEs and related brominated substances i.e. polybrominated phenols (PBPs), polybrominated anisoles (PBAs), methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and polybrominated diphenyl ethers (PBDEs) were measured in herring sampled in the northern Baltic Proper (Askö, n = 12) and the southern Bothnian Sea (Ängskärsklubb, n = 12). The geometric mean (GM) concentrations (ng/g l.w.) at Askö and Ängskärsklubb were; Σ2PBPs: 4.3 and 9.6, Σ(2)PBAs: 34 and 20, Σ(6)OH-PBDEs: 9.4 and 10, Σ(7)MeO-PBDEs: 42 and 150, Σ(6)PBDEs: 54 and 27, respectively. 6-OH-BDE47 dominated the OH-PBDE profile and comprised 87% (Askö) and 91% (Ängskärsklubb) of the ΣOH-PBDEs. At Ängskärsklubb the mean concentration of ΣMeO-PBDEs (150 ng/g l.w.) was 15 times higher than ΣOH-PBDEs. As other fish species are known to metabolically transform MeO-PBDEs to OH-PBDEs, high levels of MeO-PBDEs can be of concern as a precursor for more toxic OH-PBDEs in herring and their roe.