Bioaccumulation behaviour of polybrominated diphenyl ethers (PBDEs) in a Canadian Arctic marine food web

A comparative analysis of the bioaccumulation behaviour of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) was conducted involving simultaneous measurements of PBDE and PCB concentrations in organisms of a Canadian Arctic marine food web. Concentrations of individual PBDE congeners (BDE-28, -47, -99, -153, -154 and -183) in Arctic marine sediments (0.001-0.5 ng.g(-1) dry wt) and biota (0.1-30 ng.g(-1) wet wt) were low compared to those concentrations in biota from urbanized/industrial regions. While recalcitrant PCB congeners exhibited a high degree of biomagnification in this food web, PBDE congeners exhibited negligible biomagnification. Trophic magnification factors (TMFs) of PCBs ranged between 2.9 and 11, while TMFs of PBDEs ranged between 0.7 and 1.6. TMFs of several PBDE congeners (BDE-28, -66, -99, -100, -118, -153 and -154) were not statistically greater than 1, indicating a lack of food web magnification. BDE-47 was the only PBDE with a TMF (i.e. 1.6) statistically greater than 1, hence showing evidence of biomagnification in the food web. However, the TMF of BDE-47 (1.6) was substantially lower than TMFs of recalcitrant Cl(5)-Cl(7) PCBs (TMFs~9-11). Species-specific bioaccumulation factors (BAFs) of PBDEs in homeotherms were much smaller than those for PCBs. This further indicates the low degree or absence of biomagnification of PBDEs compared to PCBs in this food web. The field observations suggest PBDEs exhibit a relatively rapid rate of depuration though biotransformation in Arctic marine organisms, which is consistent with laboratory studies in fish and rats.     

Levels of brominated flame retardants and methoxylated polybrominated diphenyl ethers in eggs of white-tailed sea eagles breeding in different regions of Sweden

Forty-four unhatched eggs from white-tailed sea eagle (Haliaeetus albicilla), collected in four regions in Sweden in 1992-2005, were analysed for contents of polybrominated diphenyl ethers (PBDEs), polybrominated biphenyl (PBB), hexabromocyclododecane (HBCD) and naturally occurring methoxylated polybrominated diphenyl ethers (MeO-PBDEs). Two freshwater areas—Lapland in the arctic zone (LAP) and inland lakes in central and southern Sweden (INL), and two brackish marine areas in the Baltic Sea—the south Bothnian Sea (SB) and the Baltic Proper (BP)—were chosen for comparison of the concentrations and congener distributions in white-tailed sea eagles with different diet and migratory patterns. The geometric mean (GM) concentrations (ng/g lipid weight (l.w.)) of ∑₅PBDE (BDE-47, -99, -100, -153, and -154) were 720 (LAP), 1500 (INL), 4 100 (SB) and 4 300 (BP), whereas BDE-209 was not detectable in any of the samples. The GM concentrations for HBCD content in LAP, INL, SB and BP were 60, 90, 150 and 140 ng/g l.w., respectively, whereas the corresponding values for BB-153 were 20, 30, 100 and 120 ng/g l.w. In general, the eggs from all four regions demonstrated similar patterns of PBDE congeners, with concentrations in descending order of BDE-47, -100, -99, -153 and -154. The ∑₃-MeO-BDEs (6-MeO-BDE47, 2′-MeO-BDE68, 5-Cl-6-MeO-BDE47) for these same regions (as above) were 80, 40, 340 and 240 ng/g l.w., respectively. ∑₃-MeO-BDEs for LAP and INL (freshwaters) were significantly different, whereas those for SB and BP were not. The presence of MeO-PBDEs in all of the inland samples indicates that there is an as-yet-unidentified source of these compounds in the freshwater ecosystem. Between the two more contaminated subpopulations from the Baltic Sea coast, SB showed significantly lower productivity than BP, but no correlation was found between productivity and PBDE, PBB and HBCD at the concentrations found in this study.     

Bioaccumulation of polybrominated diphenyl ethers and hexabromocyclododecane in the northwest Atlantic marine food web

Seven species of teleost fishes comprising major prey of northwest Atlantic harbor seals were analyzed for polybrominated diphenyl ethers (PBDEs). PBDE concentrations in whole fish samples (n = 87) were compared with those measured previously in harbor seal blubber to evaluate the transfer of PBDEs from prey to predator. Hexabromocyclododecane (HBCD) concentrations were measured in three fish species to provide an initial estimation of HBCD contamination in this ecosystem. HBCD was detected in 87% of the fish samples at concentrations ranging from 2.4 to 38.1 ng/g, lw (overall mean 17.2 ± 10.2 ng/g, lw). ∑PBDE concentrations in fish ranged from 17.9 to 94 ng/g, lw (overall mean 62 ± 34 ng/g, lw). ∑PBDE concentrations in the harbor seals were two orders of magnitude higher than levels in the fish. Biomagnification factors (BMFs) from fish to seals averaged from 17 to 76, indicating that tetra- to hexa-BDEs are highly biomagnified in this marine food web. BDE-47 was the dominant congener in all samples, suggesting exposure to the penta-BDE mixture. The presence of higher brominated congeners including BDE-209 at measurable levels in fish and seal tissue, along with the very high biomagnification of BDE-153, as well as − 155, and − 154, suggests recent exposure to the octa- and deca-BDE formulations in this US coastal marine food web, as well as the additional contribution of BDE-209 debromination in fish to the loading of persistent PBDEs in the seals. This is the first study to report the occurrence of BDE-209 and other higher BDEs in commercially important marine fishes from the northwest Atlantic.     

Corrosion of concrete sewers--the kinetics of hydrogen sulfide oxidation

The widespread occurrence of polybrominated diphenyl ethers (PBDEs) in the environment has attracted considerable attention, leading to concerns about the extent and magnitude of wildlife and human exposure. In this work, we focus on the occurrence and fate of PBDEs in a Norwegian air-plant-herbivore-carnivore system. Specifically, we have analysed for PBDEs in moss, livers from various terrestrial herbivores (moose, grouse, and European roe deer) and, for the first time, livers from the top predator lynx. The samples were collected from different sites and time periods (1990-2004) to identify possible spatial and temporal trends in contaminant levels and patterns. The general finding was that PBDEs were found in all (biotic) samples, although at lower concentrations than previously observed in mammals from the marine environment. The PBDE levels in the herbivores ranged from less than 0.5 ng/g lipid weight to 9.4 ng/g lipid weight as the highest. The median PBDE concentration in lynx was approximately one order of magnitude higher than in the herbivores. In the lynx samples there was a predominance of BDE-153 whereas BDE-47 and 99 dominated in the herbivores. This probably reflects different bioaccumulation properties or metabolic transformation processes of the BDE-congeners, and food choice. Levels of PBDEs in both moss and herbivores showed a general decline towards the northern parts of Norway. No clear temporal trends were observed. The PBDE levels observed in this study were low and are probably of limited toxicological significance.     

Brominated flame retardants in Belgian home-produced eggs: levels and contamination sources

The extent and the sources of contamination with brominated flame retardants (BFRs), such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), in home-produced eggs from free-foraging chicken of Belgian private owners were investigated. Various factors, such as seasonal variability, exposure of chickens through diet (kitchen waste) and soil, and elimination of BFRs through eggs and faeces were assessed. PBDEs were more important than HBCD in terms of concentrations and detection frequency. Concentrations of PBDEs and HBCD in Belgian home-produced eggs were relatively low and comparable with reported levels from other European countries and the US. The concentrations of PBDEs (sum of 13 congeners, including BDE 209) ranged between not detected and 32 ng/g lipid weight (lw), with medians of 3.0 and < 2.0 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively. When present, BDE 209 was the major PBDE congener (45% of sum PBDEs). When BDE 209 was not detected, the PBDE profile was composed of PentaBDE (BDE 99 and BDE 47), with, in some cases, higher contribution of OctaBDE (BDE 183 and BDE 153). HBCD was also detected (< 0.4 and 2.9 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively), but at lower detection frequency. The highest HBCD value was 62 ng/g lw. The similarity between profiles and seasonal variations in the concentrations of BFRs in soil and eggs indicate that soil is an important source, but not the sole source, for eggs laid by free-foraging chicken. The contamination of eggs with PBDEs and HBCD appears to be of low concern for public health and the contribution of eggs to the total daily intake of PBDEs appears to be limited (10% for chicken owners and 5% for the average Belgian consumer).     

Polybrominated diphenyl ethers in sewage sludge and treated biosolids: Effect factors and mass balance

Polybrominated diphenyl ether (PBDE) flame retardants have been consistently detected in sewage sludge and treated biosolids. Two hundred and eighty-eight samples including primary sludge (PS), waste biological sludge (WBS) and treated biosolids from fifteen wastewater treatment plants (WWTPs) in Canada were analyzed to investigate the factors affecting accumulation of PBDEs in sludge and biosolids. Factors examined included environmental/sewershed conditions and operational parameters of the WWTPs. PBDE concentrations in PS, WBS and treated biosolids were 230–82,000 ng/g, 530–8800 ng/g and 420–6000 ng/g, respectively; BDE-209,-99, and -47 were the predominant congeners. Concentrations were influenced by industrial input, leachate, and temperature. Several examinations including the measurement of BDE-202 indicated minimal debromination during wastewater treatment. Estimated solids-liquid distribution coefficients were moderately correlated to hydraulic retention time, solids loading rate, mixed liquor suspended solids, solids retention time, and removal of organic solids, indicating that PBDE partitioning to solids can be optimized by WWTPs' operational conditions. Solids treatment type strongly affected PBDE levels in biosolids: 1.5 times increase after solids digestion, therefore, digestion efficiency could be a potential factor for variability of PBDEs concentration. In contrast, alkaline treatment reduced PBDE concentrations in biosolids. Overall, mass balance approaches confirmed that PBDEs were removed from the liquid stream through partitioning to solids. Variability of PBDE levels in biosolids could result in different PBDEs burdens to agricultural land, and different exposure levels to soil organisms.     

Classic and novel brominated flame retardants (BFRs) in common sole (Solea solea L.) from main nursery zones along the French coasts

Brominated flame retardants (BFRs) were investigated in juvenile common sole from nursery zones situated along the French coast in 2007, 2008 and 2009. Extensive identification was performed with regard to PBDEs, novel BFRs 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), and other non-PBDE BFRs, namely, hexabromobenzene (HBB) and 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153). Polybrominated diphenyl ether (PBDE) concentrations (Σ 14 congeners) ranged from 0.01 ng/g to 0.16 ng/g wet weight (ww) in muscle, and 0.07 ng/g to 2.8 ng/g ww in liver. Concentrations were in the lower range of those reported in the literature in other European locations. Lower PBDE concentrations, condition indices and lipid contents were observed in the Seine estuary in 2009, possibly in relation to a lower water flow. The PBDE patterns and ratios we observed suggested that juvenile sole have a relative high metabolic degradation capacity. Non-PBDE BFRs were detected at lower levels than PBDEs, i.e., within the < method detection limit - 0.005 ng/g ww range in muscle, and < method detection limit - 0.2 ng/g ww range in liver. The data obtained is of particular interest for the future monitoring of these compounds in the environment.     

Levels of brominated flame retardants and other pesistent organic pollutants in breast milk samples from Limpopo Province, South Africa

The non-occupational exposure to brominated flame retardants, and other persistent organic pollutants (POPs) was studied by collecting human breast milk samples from mothers residing in Thohoyandou area, a rural district in the Limpopo Province, northern part of South Africa (SA). Of all collected samples to be analysed (n = 28), those with large enough milk volumes, (n = 14) were quantified for polybrominated diphenyl ethers (PBDEs) (9 congeners: BDE-28, 47, 66, 99, 100, 138, 153, 154, and 183) and hexabromocyclododecane (HBCD) on a GC equipped with dual capillary columns and dual electron-capture detectors (ECD). The levels of PBDE congeners (median sumBDE 1.3 ng/g of lipids) and of HBCD were not far from levels generally found in European studies, and this study may be the first report on the presence of PBDEs and HBCD in SA breast milk. On a congener basis, the finding of comparably high BDE-183 levels suggests a specific PBDE usage, or contamination situation in SA. Apart from BFRs, the high DDT levels found in the breast milk from this area (median and maximum sumDDT levels of about 4 600 and over 20 000 ng/g of lipids, respectively; n = 28) have earlier been reported. In addition, other POPs (PCBs, HCB and HCHs) were found in SA breast milk, at relatively low levels. To conclude, measurable levels of PBDEs and HBCD, and a specific BDE congener pattern, were found in breast milk from the Limpopo province, SA. A number of other POPs, including DDTs in high levels, were also present.     

Comparisons of polybrominated diphenyl ether and hexabromocyclododecane concentrations in dust collected with two sampling methods and matched breast milk samples

Household dust from 19 Swedish homes was collected using two different sampling methods: from the occupant's own home vacuum cleaner after insertion of a new bag and using a researcher-collected method where settled house dust was collected from surfaces above floor level. The samples were analyzed for 16 polybrominated diphenyl ether (PBDE) congeners and total hexabromocyclododecane (HBCD). Significant correlations (r = 0.60-0.65, Spearman r = 0.47-0.54, P < 0.05) were found between matched dust samples collected with the two sampling methods for ∑OctaBDE and ∑DecaBDE but not for ∑PentaBDE or HBCD. Statistically significantly higher concentrations of all PBDE congeners were found in the researcher-collected dust than in the home vacuum cleaner bag dust (VCBD). For HBCD, however, the concentrations were significantly higher in the home VCBD samples. Analysis of the bags themselves indicated no or very low levels of PBDEs and HBCD. This indicates that there may be specific HBCD sources to the floor and/or that it may be present in the vacuum cleaners themselves. The BDE-47 concentrations in matched pairs of VCBD and breast milk samples were significantly correlated (r = 0.514, P = 0.029), indicating that one possible exposure route for this congener may be via dust ingestion. PRACTICAL IMPLICATIONS: The statistically significant correlations found for several individual polybrominated diphenyl ether (PBDE) congeners, ∑OctaBDE and ∑DecaBDE between the two dust sampling methods in this study indicate that the same indoor sources contaminate both types of dust or that common processes govern the distribution of these compounds in the indoor environment. Therefore, either method is adequate for screening ∑OctaBDE and ∑DecaBDE in dust. The high variability seen between dust samples confirms results seen in other studies. For hexabromocyclododecane (HBCD), divergent results in the two dust types indicate differences in contamination sources to the floor than to above-floor surfaces. Thus, it is still unclear which dust sampling method is most relevant for HBCD as well as for ∑PentaBDE in dust and, further, which is most relevant for determining human exposure to PBDEs and HBCD.     

Diastereomer-specific bioaccumulation of hexabromocyclododecane (HBCD) in a coastal food web, Western Norway

The present study reports diastereomer-specific accumulation of HBCD from a point source in five marine species representing a typical food web in a Norwegian coastal area. Samples of mussels, polychaetes, crabs and seabird eggs were analyzed for the diastereomers α-, β- and γ-HBCD, as well as lipid content and stable isotopes of nitrogen (¹⁵N/¹⁴N) to estimate trophic level. Accumulated HBCD did not correlate well with lipid content for most of the species, thus wet-weight based concentrations were included in an assessment of biomagnification. In contrast to β- and γ-HBCD, the α-diastereomer increased significantly with trophic level, resulting in magnification factors > 1 in this coastal marine ecosystem. Data for poikilotherms did not show the same positive correlation between the α-diastereomer and trophic position as homeotherms. The apparent biomagnification of the α-HBCD could be due to bioisomerization or diastereomer-specific elimination that differed between poikilotherms and homeotherms.     

Spatial diastereomer patterns of hexabromocyclododecane (HBCD) in a Norwegian fjord

Hexabromocyclododecane (HBCD) is the third most used brominated flame retardant globally, and has been found widely distributed in the environment. The present study reports concentrations and spatial patterns of α, β and γ-HBCD in a contaminated Norwegian fjord. Intertidal surface sediment and selected species from the marine food web were sampled at five locations in increasing distance from a known point source of HBCD. All sediment and biota samples were analyzed for the three HBCD diastereomers by liquid chromatography and mass spectrometry (LC/MS). The results demonstrated a HBCD gradient with decreasing concentrations at increasing distance from the point source in sediment and sedentary species, but less so in the species with large feeding ranges. Mean concentrations of ΣHBCD at the closest/most remote locations relative to the point source were 9000/300 ng g^− 1 TOC in sediment and 150/90 ng g^− 1 lw in the species with largest feeding range (great black-backed gull). The HBCD diastereomer patterns were similar for each of the matrices (sediment, organisms) independent of distance from the source, indicating no difference in environmental partitioning between the diastereomers. However, the concentration ratio of diastereomers in each matrix ranged from 3:1:10 (α:β:γ) in the sediments to 55:1 (α:γ) in the highest trophic level species, suggesting diastereomer-specific bioaccumulation in the organisms.     

上海城市污泥中HBCD的浓度及土地施用累积水平

利用索氏提取、凝胶渗透色谱及高效液相色谱/质谱联用方法分析了上海市27个污水处理厂最终污泥中六溴环十二烷(HBCD)的浓度及分布情况。结果表明,污泥中HBCD的浓度范围为0.103～37.220 ng/g干重,平均值为4.700 ng/g干重,与世界其他地区相比,污染水平较低。在其中17个样品中,γ-HBCD是主要成分(44.7%～76.3%),在其他10个样品中,α-HBCD所占比例最高(49.6%～90.6%)。据估算,上海市通过污泥每年排放HBCD的量为1.5 kg。污泥如未经处理直接进行土地施用,土壤中HBCD的残留浓度会高出近似背景区一个数量级。     

Polybrominated diphenyl ethers in road and farmland soils from an e-waste recycling region in Southern China: Concentrations, source profiles, and potential dispersion and deposition

The present study analyzed road soils collected near the dismantling workshops of an e-waste recycling region in South China to determine the PBDE profiles. Farmland soils at a distance of about 2 km from the dismantling workshops were also collected to evaluate the potential dispersion and deposition of PBDEs in the surrounding environment. Total PBDE concentrations ranged from 191 to 9156 ng/g dry weight in road soils and from 2.9 to 207 ng/g dry weight in farmland soils, respectively. Three PBDE source profiles were observed from the road soils by principal component analysis, and were compared with the congener patterns in different technical products. Elevated abundances of octa- and nona-congeners were found in the “deca-” derived PBDEs as compared with the deca-BDE products. The results in this study suggest that debromination of BDE 209 may have occurred during the use of electric and electronic equipment and/or another technical formulation (Bromkal 79-8DE) was also likely the source of octa- and nona-congeners in e-wastes. Comparison of the PBDE patterns in road and farmland soils implied that the PBDEs in farmland soils have been subject to complex environmental processes.     

Persistent organic pollutants and mercury in dead and dying glaucous gulls (Larus hyperboreus) at Bjørnøya (Svalbard)

Dead and dying glaucous gulls (Larus hyperboreus) were collected on Bjørnøya in the Barents Sea in 2003, 2004 and 2005. Autopsies of the seabirds only explained a clear cause of death for three (14%) of the 21 birds. A total of 71% of the birds were emaciated. Liver and brain samples were analysed for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ether (PBDEs), hexabromocyclododecanes (HBCDs) and mercury (Hg). High levels of ΣOCPs, ΣPCBs, ΣPBDEs and α-HBCD were found in liver and brain. Compared to the dead and dying glaucous gulls found 1989, the congeners' composition tended to change toward more persistent compounds in the 2003–2005 samples. The brain levels of OCPs and PCBs did not differ between 1989 and 2003–2005, while the liver levels were significantly lower. The brain/liver ratio for PCB and PBDE significantly decreased with halogenations of the molecule, indicating a clear discrimination of highly halogenated PCBs and PBDEs entering the brain. There was further a clear negative correlation between contaminant concentrations and body condition. The brain levels were not as high as earlier published lethal levels of p,p′-DDE or PCB. However, more recent studies reported a range of sub-lethal OCP- and PCB-related effects in randomly sampled glaucous gulls. An additional elevation of pollutants due to emaciation may increase the stress of the already affected birds. The high brain levels of OCP, PCB and PBDE of present study might therefore have contributed to the death of weakened individuals of glaucous gull.     

Levels, fluxes and time trends of persistent organic pollutants in Lake Thun, Switzerland: Combining trace analysis and multimedia modeling

Levels, mass fluxes, and time trends of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Lake Thun, a peri-Alpine lake, are investigated. We present measurements of PBDEs and PCBs in air, lake water, lake sediment, and tributary water. These measurements are combined with a multimedia fate model, based on site-specific environmental parameters from the lake catchment. Measured loadings of PBDEs and PCBs in air and tributaries were used to drive the model. The model satisfactorily reproduces PBDE and PCB congener patterns in water and sediment, but it tends to yield concentrations in water below the measurements and concentrations in sediment exceeding the measurements. A sensitivity analysis reveals that partitioning of PBDEs and PCBs between the aqueous dissolved phase and suspended particulate matter in the water column strongly affects the model results, in particular the concentrations in water and sediment. For lower-brominated PBDEs, approximately 70% and 30% of input into the lake stems from atmospheric deposition and from tributaries, respectively. For heavier PBDEs and all PCBs, rivers appear to deliver the major load (64-92%). Waste water effluents are of minor importance. 50-90% of the total input is buried in the permanent sediment. Sediment burial makes PBDEs and PCBs less available for recycling in the environment, and reduces concentrations in the outflowing river. If use of deca-BDE increases in the future, levels in Lake Thun will follow the same trend. If the use and resulting environmental emissions decrease, concentrations in water will rapidly decline, according to our calculations, while sediment levels will decrease at a considerably slower rate.     

Spatial and temporal changes of chlorinated pesticides, PCBs, dioxins (PCDDs/PCDFs) and brominated flame retardants in human breast milk from Northern Russia

This study presents for the first time temporal changes of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Russian human breast milk samples. Concentrations of OCPs and PCBs in samples from three locations in the North West of Russia in 2000-2002 (n=42), were compared to corresponding levels measured in 1993-1996 (n=58). In addition brominated flame retardants (BFRs), consisting of polybrominated diphenylethers (PBDEs) (including BDE-209) and hexabromocyclododecane (HBCD) were analysed in samples from 2000-2002 (n=37). The present levels of SigmaDDTs and SigmaHCHs were 5 and 10 times higher than corresponding levels in the neighbouring country Norway. Median concentrations of SigmaHCHs (196 microg/kg lw), SigmaCHBs (19.7 microg/kg lw) and SigmaPCBs(16) (316 microg/kg lw) were highest in Murmansk. The percentage of p,p'-DDT to SigmaDDTs and ratio DDE/DDT suggest possible ongoing use of DDT in Russia. Levels of PBDE were low and dominated by the congeners BDE-47 and BDE-153. The deca brominated BDE-209 was detected in all analysed samples (median concentration 0.19 microg/kg lipid). Levels of SigmaOCPs and SigmaPCBs decreased 56 and 30% in Murmansk and 36 and 43% in Arkhangelsk during the study period. The decline of SigmaOCPs was significant at both locations (p<0.05-p<0.0001). For SigmaPCBs, the decreasing trend was only significant in Arkhangelsk (p<0.0001). In addition, a decline of Sigmatotal TEQs (SigmaTEQs of PCDDs/PCDFs, non-ortho- and mono-ortho PCBs) was observed in Murmansk and Arkhangelsk during the study period. The exposure of infants by PCDDs/PCDFs and dioxin-like PCBs is still exceeding the daily tolerable intake (TDI) in North West Russia. However, the concentrations of PCDDs/PCDFs and dioxin-like PCBs seem to decline very rapidly.     

Decabromodiphenyl ether (BDE-209) enters the food web of the River Po and is metabolically debrominated in resident cyprinid fishes

Decabromodiphenyl ether (BDE-209), the primary constituent of a widely used flame retardant formulation, is present at relatively high levels in sediments and macroinvertebrates of the River Po. Since it was demonstrated that BDE-209 can be biotransformed to smaller and more toxic polybrominated dipheyl ethers (PBDEs), the main objective of this study was to assess whether the large quantities of BDE-209 present in the River Po are bioavailable to the higher levels of the food web and are biotransformed in feral fishes. To this aim, 23 cyprinids, mainly common carp, were analysed for the hepatic contents of PBDEs. Contrary to sediments and invertebrates of the same area, no fish sample contained detectable levels of BDE-209. All fishes contained typical PBDE representatives, e.g. BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154, but more importantly they contained three congeners, i.e. BDE-179, BDE-188 and BDE-202, which are not present in any technical formulations and are known products of BDE-209 debromination in fish. The age of carps had no effects on the bioaccumulation of PBDEs. Conversely, the contents of PCBs, which also were determined in the same fish samples, showed a positive correlation with age. Both groups of chemicals displayed a tendency to a higher contamination in male fish. This study shows that BDE-209 enters the food web of the River Po contributing to the load of lower brominated PBDEs and thus to the load of chemical stressors threatening the aquatic life of the major Italian watercourse.     

Persistent organic pollutants in ringed seals from the Russian Arctic

Organochlorine compounds total DDT (ΣDDT), total HCH isomers (ΣHCH), toxaphenes (sum of Parlar 26, 50, 62), mirex, endrin, methoxychlor, total chlorinated benzenes (ΣCBz), total chlordane compounds (ΣCHL), polychlorinated biphenyls (total of 56 congeners; ΣPCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and polybrominated diphenyl ethers (sum of 7 tri- to hepta congeners; ΣPBDEs) were analysed in the blubber of adult ringed seals from the four areas of the Russian Arctic (White Sea, Barents Sea, Kara Sea and Chukchi Sea) collected in 2001-2005. Ringed seals from the south-western part of the Kara Sea (Dikson Island — Yenisei estuary) were the most contaminated with ΣDDTs, ΣPCBs, ΣCHL, and mirex as compared with those found in the other three areas of Russian Arctic, while the highest mean concentrations of ΣHCHs and PCDD/Fs were found in the blubber of ringed seals from the Chukchi Sea and the White Sea, respectively. Among all organochlorine compounds measured in ringed seals from the European part of the Russian Arctic, concentrations of ΣDDT and ΣPCBs only were higher as compared with the other Arctic regions. Levels of all other organochlorine compounds were similar or lower than in seals from Svalbard, Alaska, the Canadian Arctic and Greenland. ΣPBDEs were found in all ringed seal samples analysed. There were no significant differences between ΣPBDE concentrations found in the blubber of ringed seals from the three studied areas of the European part of the Russian Arctic, while PBDE contamination level in ringed seals from the Chukchi Sea was 30-50 times lower. ΣPBDE levels in the blubber of seals from the European part of the Russian Arctic are slightly higher than in ringed seals from the Canadian Arctic, Alaska, and western Greenland but lower compared to ringed seals from Svalbard and eastern Greenland.     

The role of diet on long-term concentration and pattern trends of brominated and chlorinated contaminants in western Hudson Bay polar bears, 1991-2007

Adipose tissue was sampled from the western Hudson Bay (WHB) subpopulation of polar bears at intervals from 1991 to 2007 to examine temporal trends of PCB and OCP levels both on an individual and sum-(∑-)contaminant basis. We also determined levels and temporal trends of emerging polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs) and other current-use brominated flame retardants. Over the 17-year period, ∑ DDT (and p,p′-DDE, p,p′-DDD, p,p′-DDT) decreased (−8.4%/year); α-hexachlorocyclohexane (α-HCH) decreased (−11%/year); β-HCH increased (+ 8.3%/year); and ∑ PCB and ∑ chlordane (CHL), both contaminants at highest concentrations in all years (> 1 ppm), showed no distinct trends even when compared to previous data for this subpopulation dating back to 1968. Some of the less persistent PCB congeners decreased significantly (−1.6%/year to −6.3%/year), whereas CB153 levels tended to increase (+ 3.3%/year). Parent CHLs (c-nonachlor, t-nonachlor) declined, whereas non-monotonic trends were detected for metabolites (heptachlor epoxide, oxychlordane). ∑ chlorobenzene, octachlorostyrene, ∑ mirex, ∑ MeSO₂-PCB and dieldrin did not significantly change. Increasing ∑ PBDE levels (+ 13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(α)-HBCD was only detected post-2000. Levels of the highest concentration brominated contaminant, BB153, showed no temporal change. As long-term ecosystem changes affecting contaminant levels may also affect contaminant patterns, we examined the influence of year (i.e., aging or “weathering” of the contaminant pattern), dietary tracers (carbon stable isotope ratios, fatty acid patterns) and biological (age/sex) group on congener/metabolite profiles. Patterns of PCBs, CHLs and PBDEs were correlated with dietary tracers and biological group, but only PCB and CHL patterns were correlated with year. DDT patterns were not associated with any explanatory variables, possibly related to local DDT sources. Contaminant pattern trends may be useful in distinguishing the possible role of ecological/diet changes on contaminant burdens from expected dynamics due to atmospheric sources and weathering.     

Arctic marine ecosystem contamination.

The current state of knowledge of levels, spatial and temporal trends of contaminants in the Arctic marine ecosystem varies greatly among pollutants and among environmental compartments. Levels of polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and some heavy metals such as mercury and lead, in Arctic marine mammals and fish are relatively well documented because of the need for comparisons with biota in more polluted environments and interest in the contamination of native diets. Levels of heavy metals, alkanes, polyaromatic hydrocarbons (PAH) and OCs in the Arctic Ocean are comparable to uncontaminated ocean waters in the mid-latitudes. But concentrations of alpha- and gamma-hexachlorocyclohexane (HCHs) are higher in northern waters far removed from local sources, possibly because lower water temperature reduces transfer to the atmosphere. Bioaccumulation of OCs and heavy metals in Arctic marine food chains begins with epontic ice algae or phytoplankton in surface waters. Polychlorinated camphenes (PCC), PCBs, DDT- and chlordane-related compounds are the major OCs in marine fish, mammals and seabirds. Mean concentrations of most PCBs and OC pesticides in ringed seal (Phoca hispida) and polar bear (Ursus maritimus) populations in the Canadian Arctic are quite similar indicating a uniform geographic distribution of contamination, although alpha-HCH showed a distinct latitudinal gradient in bears due to higher levels in zones influenced by continental runoff. Ringed seals from Spitzbergen have higher levels of PCBs, total DDT and polychlorinated dioxins/furans (PCDD/PCDFs). In contrast to other OCs, PCDD/PCDFs in Canadian Arctic ringed seals and polar bears were higher in the east/central Arctic than at more southerly locations. Remarkably high cadmium levels are found in kidney and liver of narwhal (Monodons monoceros) from western Baffin Bay (mean of 63.5 micrograms g-1) and western Greenland waters (median of 39.5 micrograms g-1). Mercury concentrations in muscle of ringed seal and cetaceans frequently exceed 0.5 microgram g-1 especially in older animals. Cadmium concentrations in polar bear liver increased from west to east, while mercury levels were higher in ringed seals from the western Canadian Arctic, which suggests that natural sources of these metals predominate. Studies of temporal trends in OCs in ringed seals and seabirds in the Canadian Arctic indicate PCB and DDT levels declined significantly from the early 1970s to the 1980s. There is a lack of temporal trend data for other OC pesticides as well as for heavy metals and hydrocarbons.(ABSTRACT TRUNCATED AT 400 WORDS)