Brominated flame retardants in the Arctic environment — trends and new candidates

Polybrominated diphenyl ethers (PBDEs) containing two to 10 bromines are ubiquitous in the Arctic, in both abiotic and biotic samples. Hexabromocyclododecane (HBCD) is also ubiquitous in the Arctic, with the γ-HBCD isomer predominating in air, the α-HBCD isomer predominating in biota and similar concentrations of α-, β- and γ-HBCD found in marine sediments. Other brominated flame retardants (BFRs) found in some Arctic samples are polybrominated biphenyls (PBBs), tetrabromobisphenol A (TBBPA), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HxBBz), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH). Temporal trends of tetra- to heptaBDEs and HBCD show increasing concentrations or a tendency to levelling off depending on the matrix (air, sediment, biota) and location, but no uniform picture for the Arctic emerges. BDE-209 concentrations are increasing in air. PBDEs and HBCD spatial trends in seabirds and marine mammals are similar to those seen previously for polychlorinated biphenyls (PCBs), with highest concentrations found in organisms from East Greenland and Svalbard. These trends indicate western Europe and eastern North America as important source regions of these compounds via long range atmospheric transport and ocean currents. Latitudinal trends showed lower concentrations and fluxes of PBDEs at higher latitudes. The tetra-hexaBDEs and α-HBCD biomagnify in Arctic food webs. Results for BDE-209 are more conflicting, showing either only low or no biomagnification potential. PBDE and HBCD concentrations are lower in terrestrial organisms and higher in marine top predators such as some killer whale populations in Alaska and glaucous gulls from the Barents Sea area. Higher concentrations are seen near populated areas indicating local sources. Findings of BTBPE, HxBBz, PBEB, PBT and TBECH in seabirds and/or marine mammals indicate that these compounds reach the Arctic, most probably by long range atmospheric transport and accumulate in higher trophic level organisms and that increasing use as PBDE replacements will lead to increasing concentrations.     

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.     

Influence of biological and ecological factors on the bioaccumulation of polybrominated diphenyl ethers in aquatic food webs from French estuaries

Previous studies have shown the worldwide presence of six congeners of polybrominated diphenyl ethers (PBDEs) in marine biota (BDE-28, -47, -99, -100, -153 and -154). The objective of the present study was to document their presence, their level and their transfer in the food web of two major estuaries in France, the Loire and the Seine. PBDEs were quantified in eight principal species from the Loire, representing primary consumers (the bivalve Scrobicularia plana), omnivores (the worm Nereis diversicolor, the shrimps Crangon crangon, Palaemon elegans and Palaemon serratus, the flatfish Platichthys flesus and Solea solea) and supercarnivores (the eel Anguilla anguilla). In the Seine, only worms, bivalves, sole and eels have been studied. Parameters, which can interfere with the interpretation of contamination data (organ distribution, influence of weight or size of specimens, lipid richness, intrinsic variability), have been examined. BDE-47 was the predominant congener in all biota. Higher contamination was observed in most of the species collected from the Seine, in agreement with the higher human presence and economic activity in the Seine than in the Loire basin. PBDEs have been shown to biomagnify in both of the studied estuarine food webs. However, assessment of PBDE transfer from seafood products exposed to contaminants in the Seine estuary showed that human daily intake is far below the no observed adverse effect levels.     

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.     

Biomagnification of PBDEs and PCBs in food webs from the Baltic Sea and the northern Atlantic Ocean

Biomagnification of polychlorinated biphenyls (PCBs) and polybrominated diphenylethers (PBDEs) in food webs from the Baltic Sea and the northern Atlantic Sea was investigated. For this, we used PCB and PBDE concentration data, together with data on fish body weight and delta15N of fish and zooplankton as a measure of trophic position. In the Baltic Sea material, consisting of zooplankton, sprat, herring and salmon, we report biomagnification of all PCB congeners but PCB #209 and of PBDEs with 3-6 or 7 bromine atoms. Higher brominated PBDEs and PCB 209 did not biomagnify likely due to their high molecular weights or sizes and subsequent inefficient dietary uptake in fish. If salmon was excluded from the statistical analysis, strong biomagnification of PCB #209 was evident, indicating species differences in biomagnification. In the Baltic Sea material delta15N and body weight covaried. In the Atlantic Sea material, consisting of fish samples (herring and salmon) of larger body sizes, we show positive correlation between concentrations of most PCBs and PBDEs and body weight without increasing delta15N. This shows that biomagnification in some cases depends on body size and not trophic position. We conclude that there probably is trophic position dependence in biomagnification, which was manifested in a food chain from zooplankton to piscivores, but no further trophic position influence on biomagnification in fish at the highest trophic levels. In these fish, there was a body size effect leading to biomagnification, probably due to slower clearance in larger fish. PCB concentrations were generally between 2 and 6 times higher in Baltic Sea salmon than in Atlantic Sea salmon. Higher PBDE concentrations in the Baltic compared to the Atlantic Sea salmon were also found, but with a larger variation between congeners. Nona- to deca-BDEs were found in most investigated samples, which illustrates the bioavailability of these compounds. Unidentified penta-, hexa-, hepta-, and octa- BDEs were found in several samples.     

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.     

Chlorobenzenes, chlorinated pesticides, coplanar chlorobiphenyls and other organochlorine compounds in Greenland biota

This paper summarises the levels and composition of chlorobenzenes, chlorinated pesticides, coplanar polychlorinated biphenyls (PCBs) and the chlorinated compounds octachlorostyrene (OCS), hexachlorocyclobutadiene (HCBD) and pentachloro-anisole (PCA) in biota from the terrestrial, freshwater and marine environment of Greenland. The data were obtained during the second phase of the Arctic Monitoring and Assessment Programme (AMAP). Of the chlorobenzenes, hexachlorobenzene was the main constituent detected in almost all samples. The chlorobenzenes accumulate in the marine food web in a similar manner to the better-studied persistent organic pollutants, with maximum concentrations in beluga, minke whale and narwhal. However, concentrations in ringed seals and kittiwakes were lower than in marine fish, contradicting biomagnification. Of the organochlorine pesticides, the drin pesticides (aldrin, endrin, dieldrin) and heptachlor had increasing concentrations along the food chain, whilst biomagnification was less pronounced for endosulfan, methoxychlor and mirex. Endosulfan and methoxychlor are pesticides still in use and considered less persistent than other organochlorine pesticides. Their occurrence in Arctic biota is of particular concern, also given the high acute toxicity of endosulfan to fish. Chlorobenzene and pesticide concentrations tended to be lower in the Greenland samples than in the same animals from the Canadian Arctic, whilst their concentrations were similar to samples from Svalbard and Iceland. However, temporal trends might overlap the geographical differences. Coplanar chlorobiphenyls (CBs) were found in all samples analysed, with the maximum concentrations found in marine mammals such as beluga and narwhal. Biota from the terrestrial environment appeared to be less contaminated. The main contributor on a TEQ basis was CB126. OCS, HCBD and PCA were detected in biota from Greenland, although at very low concentrations. OCS seems to have the widest occurrence and the highest potential for biomagnification of the three compounds analysed.     

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.     

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.     

Burdens of PBBs, PBDEs, and PCBs in tissues of the cancer patients in the e-waste disassembly sites in Zhejiang, China

This study was conducted to explore the burdens of PBBs, PBDEs, and PCBs among cancer patients living in the e-waste disassembly sites. The contents of 23 PBB congeners, 12 PBDE congeners, and 27 PCB congeners in kidney, liver, and lung samples were measured by GC-MS. The results showed that low-brominated PBBs and PBB153 were the predominant congeners. PBDE47 were the most predominant PBDE congeners. PBDE209 were detected in > 70% of the samples, with geometric means ranging from 64.2 to 113.9 ng g^− 1 lipid. Among the three subfamilies of PHAHs, PCB concentrations were the highest. The detected levels of PHAHs were in the same order of magnitude in the three tissues, which indicated that any of the three tissues could be the suitable indicator for assessing body burdens of PHAHs. PBB contents (181-192 ng g^− 1 lipid) were obviously higher than those reported in the general USA population (3-8 ng g^− 1 lipid). PBDE levels (174.1-182.3 ng g^− 1 lipid) were comparable to those reported in the USA population, but significantly higher than those of the European population. PCBs levels were comparable to those of the European population. The high cancer incidence in the disassembly sites may be related to higher burdens of PBBs, PBDEs, and PCBs in tissues.     

A comparison of PCB bioaccumulation factors between an arctic and a temperate marine food web

To test how environmental conditions in the Arctic and the resulting ecological adaptations affect accumulation of persistent organic pollutants (POPs) in the marine food web, bioaccumulation of four polychlorinated biphenyls (PCBs) in an arctic (Barents Sea 77 °N-82 °N) and a temperate marine (Baltic Sea 54 °N-62 °N) food web were compared. Three different trophic levels were studied (zooplankton, fish, and seal), representing the span from first-level consumer to top predator. Previously published high-quality data on PCB water concentrations in the two areas were used for calculation of bioaccumulation factors (BAF). BAF was calculated as the ratio of the PCB concentration in the organism ([PCB]_org; pg/kg lipid) to the dissolved water concentration (C_w; pg/L). The BAF_Arctic:BAF_Temperate ratios were above 1 for all four PCB congeners in zooplankton (6.4-13.8) and planktivorous fish (2.9-5.0)), whereas the ratios were below 1 in seal. The mean ratio between arctic and temperate BAFs for all trophic levels and congeners (BAF_Arcti:BAF_Temperate) was 4.8. When the data were corrected for the seawater temperature difference between the two ecosystems, the ratio was 2.0. We conclude that bioaccumulation differences caused by ecological or physiological adaptations of organisms between the two ecosystems were well within a water concentration variability of 50%. Further, our data support the hypothesis that lower seawater temperature lead to a thermodynamically favoured passive partitioning to organic matrices and thus elevated ambient BAFs in the Arctic compared to the Baltic Sea. This would imply that bioaccumulation in the Arctic may be described in the same way as bioaccumulation in temperate regions, e.g. by the use of mechanistic models parameterised for the Arctic.     

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.     

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.     

Trophodynamics of mercury and other trace elements in a pelagic food chain from the Baltic Sea

Mercury (Hg) and 13 other trace elements (Al, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Cd, and Pb) were measured in phytoplankton, zooplankton, mysis and herring in order to examine the trophodynamics in a well-studied pelagic food chain in the Baltic Sea. The fractionation of nitrogen isotopes (δ¹⁵N) was used to evaluate food web structure and to estimate the extent of trophic biomagnification of the various trace elements. Trophic magnification factors (TMFs) for each trace element were determined from the slope of the regression between trace element concentrations and δ¹⁵N. Calculated TMFs showed fundamental differences in the trophodynamics of the trace elements in the pelagic food chain studied. Concentrations of Al, Fe, Ni, Zn, Pb and Cd showed statistically significant decreases (TMF < 1) with increasing trophic levels and thus these trace elements tropically dilute or biodilute in this Baltic food chain. Cu, As, Cr, Mn, V, Ti and Co showed no significant relationships with trophic levels. Hg was unique among the trace elements studied in demonstrating a statistically significant increase (TMF > 1) in concentration with trophic level i.e. Hg biomagnifies in this Baltic food chain. The estimated TMF for Hg in this food chain was comparable to TMFs observed elsewhere for diverse food chains and locations.     

Evidence for higher biomagnification factors of lower chlorinated PCBs in cultivated seabass

Thirty three PCB congeners were analyzed in three size classes of seabass (Dicentrarchus labrax), from a semi-intensive fish farm, in food and in abiotic compartment. Water and suspended particulated matter (SPM) showed higher concentrations of lower chlorinated PCBs, whereas fish tissues and food showed higher concentrations of CB153 and CB138. In order to examine the influence of different inputs to seabass contamination, bioaccumulation factors (BAF), biota-suspended particulate matter bioaccumulation factors (BSMAF) and biomagnification factors (BMF) were calculated. In general, the log BAF and log BSMAF showed good correlations with log K(ow), for congeners with log K(ow)>6.1. In three fish size classes, PCB congeners with log K(ow)<6.1 were found at concentrations higher than what was expected based on the BAF calculated for the more hydrophobic congeners, suggesting a different contribution of sources. The application of a mass balance model for accumulation of some congeners in seabass estimated concentrations in fish 3- to 38-fold higher than the measured values, probably by overestimating gill absorption. The model was applied with other scenarios in order to maximize uptake from food, which may have a significant influence in accumulation, and not only from diet pellets. Its contribution to fish contamination for highly chlorinated PCBs may reach a maximum of 54-64%, and for lower chlorinated PCBs its contribution is lower than 20%. In this work it was proved that to reduce fish contamination the quality of the water should be controlled.     

Exposure and effects assessment of persistent organohalogen contaminants in arctic wildlife and fish

Persistent organic pollutants (POPs) encompass an array of anthropogenic organic and elemental substances and their degradation and metabolic byproducts that have been found in the tissues of exposed animals, especially POPs categorized as organohalogen contaminants (OHCs). OHCs have been of concern in the circumpolar arctic for decades. For example, as a consequence of bioaccumulation and in some cases biomagnification of legacy (e.g., chlorinated PCBs, DDTs and CHLs) and emerging (e.g., brominated flame retardants (BFRs) and in particular polybrominated diphenyl ethers (PBDEs) and perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanic acid (PFOA) found in Arctic biota and humans. Of high concern are the potential biological effects of these contaminants in exposed Arctic wildlife and fish. As concluded in the last review in 2004 for the Arctic Monitoring and Assessment Program (AMAP) on the effects of POPs in Arctic wildlife, prior to 1997, biological effects data were minimal and insufficient at any level of biological organization. The present review summarizes recent studies on biological effects in relation to OHC exposure, and attempts to assess known tissue/body compartment concentration data in the context of possible threshold levels of effects to evaluate the risks. This review concentrates mainly on post-2002, new OHC effects data in Arctic wildlife and fish, and is largely based on recently available effects data for populations of several top trophic level species, including seabirds (e.g., glaucous gull (Larus hyperboreus)), polar bears (Ursus maritimus), polar (Arctic) fox (Vulpes lagopus), and Arctic charr (Salvelinus alpinus), as well as semi-captive studies on sled dogs (Canis familiaris). Regardless, there remains a dearth of data on true contaminant exposure, cause-effect relationships with respect to these contaminant exposures in Arctic wildlife and fish. Indications of exposure effects are largely based on correlations between biomarker endpoints (e.g., biochemical processes related to the immune and endocrine system, pathological changes in tissues and reproduction and development) and tissue residue levels of OHCs (e.g., PCBs, DDTs, CHLs, PBDEs and in a few cases perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs)). Some exceptions include semi-field studies on comparative contaminant effects of control and exposed cohorts of captive Greenland sled dogs, and performance studies mimicking environmentally relevant PCB concentrations in Arctic charr. Recent tissue concentrations in several arctic marine mammal species and populations exceed a general threshold level of concern of 1 part-per-million (ppm), but a clear evidence of a POP/OHC-related stress in these populations remains to be confirmed. There remains minimal evidence that OHCs are having widespread effects on the health of Arctic organisms, with the possible exception of East Greenland and Svalbard polar bears and Svalbard glaucous gulls. However, the true (if any real) effects of POPs in Arctic wildlife have to be put into the context of other environmental, ecological and physiological stressors (both anthropogenic and natural) that render an overall complex picture. For instance, seasonal changes in food intake and corresponding cycles of fattening and emaciation seen in Arctic animals can modify contaminant tissue distribution and toxicokinetics (contaminant deposition, metabolism and depuration). Also, other factors, including impact of climate change (seasonal ice and temperature changes, and connection to food web changes, nutrition, etc. in exposed biota), disease, species invasion and the connection to disease resistance will impact toxicant exposure. Overall, further research and better understanding of POP/OHC impact on animal performance in Arctic biota are recommended. Regardless, it could be argued that Arctic wildlife and fish at the highest potential risk of POP/OHC exposure and mediated effects are East Greenland, Svalbard and (West and South) Hudson Bay polar bears, Alaskan and Northern Norway killer whales, several species of gulls and other seabirds from the Svalbard area, Northern Norway, East Greenland, the Kara Sea and/or the Canadian central high Arctic, East Greenland ringed seal and a few populations of Arctic charr and Greenland shark.     

Comparing measured and predicted PCB concentrations in Arctic seawater and marine biota

When a mechanistic food web model was parameterized for the Arctic marine ecosystem, it predicted PCB concentrations in zooplankton and fish that were two orders of magnitude lower than measured. PCB concentrations measured in zooplankton and fish were within the laboratory's accredited quality assured criteria, and were comparable to other Arctic regions. Although on a different scale, the predicted and measured PCB concentrations were highly correlated. As sensitivity analyses indicated water concentrations as the most sensitive parameter for the model output, dissolved water concentrations were predicted using measured zooplankton and air PCB concentrations, and empirical and mechanistic models. The food web model and the empirical relationship between bioaccumulation factor and octanol-water partitioning coefficient predicted mean dissolved water concentrations of 28 and 29 pg/L sum of PCB6 (PCB-28, -52, -105, -118, -138, -153), respectively. Mean dissolved water concentration predicted from measured air concentrations in 1996 was 7.6 pg/L sum of PCB5 (PCB-28 was not analysed). Mean dissolved water concentration measured in Barents Sea water sampled simultaneously as the biota in 1999 was 0.3 pg/L sum of PCB6. The dissolved water concentrations predicted from zooplankton PCB concentrations were comparable to water concentrations measured in 1996, whereas the dissolved water concentrations measured in 1999 were comparable to measurements from 2001. If the present high empirically derived bioaccumulation factors (log BAF 7.3-9.0) were realistic, this suggests that bioaccumulation in Arctic zooplankton is more efficient that previously assumed. The present study illustrates and discusses some of the difficulties encountered when different approaches to study environmental distribution of contaminants are compared.     

Age and trophic position dominate bioaccumulation of mercury and organochlorines in the food web of Lake Washington

Understanding the mechanisms of bioaccumulation in food webs is critical to predicting which food webs are at risk for higher rates of bioaccumulation that endanger the health of upper-trophic predators, including humans. Mercury and organochlorines were measured concurrently with stable isotopes of nitrogen and carbon in key fishes and invertebrates of Lake Washington to explore important pathways of bioaccumulation in this food web. Across the food web, age and trophic position together were highly significant predictors of bioaccumulation. Trophic position was more important than age for predicting accumulation of mercury, sigmaDDT, and sigma-chlordane, whereas age was more important than trophic position for predicting sigmaPCB. Excluding age from the analysis inflated the apparent importance of trophic position to bioaccumulation for all contaminants. Benthic and pelagic habitats had similar potential to bioaccumulate contaminants, although higher sigma-chlordane concentrations in organisms were weakly associated with more benthic carbon signals. In individual fish species, contaminant concentrations increased with age, size, and trophic position (delta15N), whereas relationships with carbon source (delta13C) were not consistent. Lipid concentrations were correlated with contaminant concentrations in some but not all fishes, suggesting that lipids were not involved mechanistically in bioaccumulation. Contaminant concentrations in biota did not vary among littoral sites. Collectively, these results suggest that age may be an important determinant of bioaccumulation in many food webs and could help explain a significant amount of the variability in apparent biomagnification rates among food webs. As such, effort should be made when possible to collect information on organism age in addition to stable isotopes when assessing food webs for rates of biomagnification.     

Accumulation and mother-to-calf transfer of anthropogenic and natural organohalogens in killer whales (Orcinus orca) stranded on the Pacific coast of Japan

Blubber samples were analyzed for anthropogenic and natural persistent organohalogens in nine killer whales (Orcinus orca) stranded on the northern coast of Japan in 2005. Anthropogenic organohalogens were dominated by DDTs (40-240 µg/g lipid weight (lw)), PCBs (19-68 µg/g lw), and chlordanes (trans-nonachlor, 15-80 µg/g lw). Polybrominated diphenyl ethers (PBDEs) were detected at a range of 0.22-0.64 µg/g lw (BDE-47, 42-74% of ΣPBDE). For natural organohalogens, mixed halogenated dimethylbipyrroles (Br₄Cl₂-DBP, 6.4-26 µg/g lw), heptachlorinated methylbipyrrole (Cl₇-MBP, 0.5-1.9 µg/g lw), two methoxylated tetrabromodiphenyl ethers (6-MeO-BDE47, 0.11-0.58 µg/g lw; 2'-MeO-BDE68, 0.02-0.06 µg/g lw), and dimethoxylated tetrabromobiphenyl (2,2'-diMeO-BB80, 0.06-0.20 µg/g lw) were present. These concentrations in the blubber were higher in calves than in lactating females, indicating that large quantities of the persistent organohalogens transferred from the mother to the calf through lactation. The mother-to-calf transfer ratios of PCBs and PBDEs were significantly decreased with increasing number of halogen substituents, suggesting that higher halogenated congeners are less transferable.     

PBBs, PBDEs, and PCBs levels in hair of residents around e-waste disassembly sites in Zhejiang Province, China, and their potential sources

This study was conducted to explore the exposure potential of Chinese residents to PBBs, PBDEs, and PCBs in e-waste disassembly sites in Zhejiang province. The contents of 23 PBB congeners, 12 PBDE congeners, and 27 PCB congeners in hair and in their potential sources, including soil and e-waste, were measured via GC-MS. The levels of PHAHs in the three subfamilies (i.e., the PBBs, PBDEs, and PCBs) were all considerably higher (P<0.05) in hair samples collected from the disassembly sites than from the control site. The highest levels of PBBs (57.77 ng g(-1) dw), PBDEs (29.64 ng g(-1) dw), and PCBs (181.99 ng g(-1) dw) in hair were all found in those from the disassembly site Xinqiu, which are respectively 2, 2, and 10 times more than those observed in hair from the control site Yandang. Among the three subfamilies of PHAHs, PCBs were the most predominant pollutants detected. PBBs, which have very limited information available in China, can be detected at a comparable level with PBDEs in these samples in the study. Therefore, these observations suggested that more attention should be given over the potential for environmental or occupational exposure to PHAHs present in e-waste. By and large, the PHAH levels measured in the hair samples were consistent with those detected in the soil. Hair analysis could thus be a valid screening tool for assessing human PHAHs exposure in and around e-waste disassembly sites.