(Table 1) Concentrations of organic pollutants in soil samples from Adélie penguin (Pygoscelis adeliae) colonies and reference sites, Hop Island, Antarctica

Although long-range atmospheric transport has been described as the predominant mechanism for exposing polar regions to persistent organic pollutants (POPs), recent studies have suggested that bird activity can also contribute substantially to contaminant levels in some environments. However, because the species so far reported have all been migratory, it has not been demonstrated conclusively whether locally elevated contamination represents transport from lower latitudes by the migrating birds or, alternatively, redistribution and concentration of contaminants that were already present in the high-latitude environments. The present study demonstrates, for the first time, that several POPs are present in elevated concentrations in an environment frequented by a non-migratory species (Adelie penguins) that spends its entire life in the Antarctic. Levels of POPs, such as p,p'-DDE, hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs), were 10 to 100-fold higher in soil samples from penguin colonies than from reference areas. This significant difference is likely related to local penguin activity, such as a higher abundance of guano and the presence of bird carcasses. This hypothesis is also supported by a higher percentage of persistent congeners (PCB 99, 118, 138 and 153) in the soil from the colonies compared to the reference areas. This profile of PCB congeners closely matched profiles seen in penguin eggs or penguin blood.

Dioxin-like and non-dioxin like contaminants in the herring Clupea harengus in the Norwegian and North Sea

The Norwegian spring spawning (NSS) herring is an ecologically important fish stock in the Norwegian Sea, and with a catch volume exceeding one million tons a year it is also economically important and a valuable food source. In order to provide a baseline of the levels of contaminants in this fish stock, the levels of organohalogen compounds were determined in 800 individual herring sampled at 29 positions in the Norwegian Sea and off the coast of Norway. Due to seasonal migration, the herring were sampled where they were located during the different seasons. Concentrations of dioxins and dioxin-like PCBs, non-dioxin-like PCBs (PCB7) and PBDEs were determined in fillet samples of individual herring, and found to be relatively low, with means (min-max) of 0.77 (0.24-3.5) ngTEQ/kg wet weight (ww), 5.0 (1.4-24) µg/kg ww and 0.47 (0.091-3.1) µg/kg ww, respectively. The concentrations varied throughout the year due to the feeding- and spawning cycle: Starved, pre-spawning herring caught off the Norwegian coast in January-February had the highest levels and those caught in the Norwegian Sea in April-June, after further starvation and spawning, had the lowest levels. These results show that the concentrations of organohalogen compounds in NSS herring are relatively low and closely tied to their physiological condition, and that in the future regular monitoring of NSS herring should be made in the spawning areas off the Norwegian coast in late winter.

(Table 1) Concentration of PCB and other contaminants in blood plasma of polar bears (Ursus maritimus) from Svalbard

Persistent chemicals accumulate in the arctic environment due to their chemical reactivity and physicochemical properties and polychlorinated biphenyls (PCBs) are the most concentrated pollutant class in polar bears (Ursus maritimus). Metabolism of PCB and polybrominated biphenyl ether (PBDE) flame-retardants alter their toxicological properties and these metabolites are known to interfere with the binding of thyroid hormone (TH) to transthyretin (TTR) in rodents and humans. In polar bear plasma samples no binding of [125I]-T4 to TTR was observed after incubation and PAGE separation. Incubation of the plasma samples with [14C]-4-OH-CB107, a compound with a higher binding affinity to TTR than the endogenous ligand T4 resulted in competitive binding as proven by the appearance of a radio labeled TTR peak in the gel. Plasma incubation with T4 up to 1 mM, a concentration that is not physiologically relevant anymore did not result in any visible competition. These results give evidence that the binding sites on TTR for T4 in wild living polar bears are completely saturated. Such saturation of binding sites can explain observed lowered levels of THs and could lead to contaminant transport into the developing fetus.

Persistent organic pollutants, d13C and d15N in zooplankton, fish and bird species in Kongsfjorden according to season

Seasonality in biomagnification of persistent organic pollutants (POPs; polychlorinated biphenyls, chlorinated pesticides, and brominated flame retardants) in Arctic marine pelagic food webs was investigated in Kongsfjorden, Svalbard, Norway. Trophic magnification factors (TMFs; average factor change in concentration between two trophic levels) were used to measure food web biomagnification in biota in May, July, and October 2007. Pelagic zooplankton (seven species), fish (five species), and seabirds (two species) were included in the study. For most POP compounds, highest TMFs were found in July and lowest were in May. Seasonally changing TMFs were a result of seasonally changing POP concentrations and the d15N-derived trophic positions of the species included in the food web. These seasonal differences in TMFs were independent of inclusion/exclusion of organisms based on physiology (i.e., warm- versus cold-blooded organisms) in the food web. The higher TMFs in July, when the food web consisted of a higher degree of boreal species, suggest that future warming of the Arctic and increased invasion by boreal species can result in increased food web magnification. Knowledge of the seasonal variation in POP biomagnification is a prerequisite for understanding changes in POP biomagnification caused by climate change.

(Tables 1,2) Polar bear (Ursus maritimus), beluga whale (Delphinapterus leucas) and ringed seal (Pusa hispida) liver microsomal protein content and EROD activity

The present study assessed and compared the oxidative and reductive biotransformation of brominated flame retardants, including established polybrominated diphenyl ethers (PBDEs) and emerging decabromodiphenyl ethane (DBDPE) using an in vitro system based on liver microsomes from various arctic marine-feeding mammals: polar bear (Ursus maritimus), beluga whale (Delphinapterus leucas), and ringed seal (Pusa hispida), and in laboratory rat as a mammalian model species. Greater depletion of fully brominated BDE209 (14-25% of 30pmol) and DBDPE (44-74% of 90pmol) occurred in individuals from all species relative to depletion of lower brominated PBDEs (BDEs 99,100, and 154; 0-3% of 30pmol). No evidence of simply debrominated metabolites was observed. Investigation of phenolic metabolites in rat and polar bear revealed formation of two phenolic, likely multiply debrominated, DBDPE metabolites in polar bear and one phenolic BDE154 metabolite in polar bear and rat microsomes. For BDE209 and DBDPE, observed metabolite concentrations were low to nondetectable, despite substantial parent depletion. These findings suggested possible underestimation of the ecosystem burden of total-BDE209, as well as its transformation products, and a need for research to identify and characterize the persistence and toxicity of major BDE209 metabolites. Similar cause for concern may exist regarding DBDPE, given similarities of physicochemical and environmental behavior to BDE209, current evidence of biotransformation, and increasing use of DBDPE as a replacement for BDE209.

(Table 1) Neutral and phenolic organohalogen compounds in blubber samples of ringed seals (Pusa hispida) from East Greenland

We report on the comparative bioaccumulation, biotransformation and/or biomagnification from East Greenland ringed seal (Pusa hispida) blubber to polar bear (Ursus maritimus) tissues (adipose, liver and brain) of various classes and congeners of persistent chlorinated and brominated contaminants and metabolic by-products: polychlorinated biphenyls (PCBs), chlordanes (CHLs), hydroxyl (OH-) and methylsulfonyl (MeSO2-) PCBs, polybrominated biphenyls (PBBs), OH-PBBs, polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants and OH- and methoxyl (MeO-) PBDEs, 2,2-dichloro-bis(4-chlorophenyl)ethene (p,p'-DDE), 3-MeSO2-p,p'-DDE, pentachlorophenol (PCP) and 4-OH-heptachlorostyrene (4-OH-HpCS). We detected all of the investigated contaminants in ringed seal blubber with high frequency, the main diet of East Greenland bears, with the exception of OH-PCBs and 4-OH-HpCS, which indicated that these phenolic contaminants were likely of metabolic origin and formed in the bears from accumulated PCBs and octachlorostyrene (OCS), respectively, rather than being bioaccumulated from a seal blubber diet. For all of the detectable sum of classes or individual organohalogens, in general, the ringed seal to polar bear mean BMFs for SumPCBs, p,p'-DDE, SumCHLs, SumMeSO2-PCBs, 3-MeSO2-p,p'-DDE, PCP, SumPBDEs, total-(alpha)-HBCD, SumOH-PBDEs, SumMeO-PBDEs and SumOH-PBBs indicated that these organohalogens bioaccumulate, and in some cases there was tissue-specific biomagnification, e.g., BMFs for bear adipose and liver ranged from 2 to 570. The blood-brain barrier appeared to be effective in minimizing brain accumulation as BMFs were <= 1 in the brain, with the exception of SumOH-PBBs (mean BMF = 93±54). Unlike OH-PCB metabolites, OH-PBDEs in the bear tissues appeared to be mainly accumulated from the seal blubber rather than being metabolic formed from PBDEs in the bears. In vitro PBDE depletion assays using polar bear hepatic microsomes, wherein the rate of oxidative metabolism of PBDE congeners was very slow, supported the probability that accumulation from seals is the main source of OH-PBDEs in the bear tissues. Our findings demonstrated from ringed seal to polar bears that organohalogen biotransformation, bioaccumulation and/or biomagnification varied widely and depended on the contaminant in question. Our results show the increasing complexity of bioaccumulated and in some cases biomagnified, chlorinated and brominated contaminants and/or metabolites from the diet may be a contributing stress factor in the health of East Greenland polar bears.

Thyroid hormones and halogenated organic compounds in black-legged kittiwake (Rissa tridactyla) and northern fulmar (Fulmarus glacialis)

Thyroid hormones are essential for normal growth and development and disruption of thyroid homeostasis can be critical to young developing individuals. The aim of the present study was to assess plasma concentrations of halogenated organic contaminants (HOCs) in chicks of two seabird species and to investigate possible correlations of HOCs with circulating thyroid hormone (TH) concentrations. Plasma from black-legged kittiwake (Rissa tridactyla) and northern fulmar (Fulmarus glacialis) chicks were sampled in Kongsfjorden, Svalbard in 2006. The samples were analyzed for thyroid hormones and a wide range of HOCs (polychlorinated biphenyls (PCBs), hydroxylated (OH-) and methylsulphoned (MeSO-) PCB metabolites, organochlorine pesticides (OCPs), brominated flame retardants (BFRs), and perfluorinated compounds (PFCs)). Concentrations of HOCs were generally low in kittiwake and fulmar chicks compared to previous reports. HOC concentrations were five times higher in fulmar chicks compared to in kittiwake chicks. PFCs dominated the summed HOCs concentrations in both species (77% in kittiwakes and 69% in fulmars). Positive associations between total thyroxin (TT4) and PFCs (PFHpS, PFOS, PFNA) were found in both species. Although correlations do not implicate causal relationships per se, the correlations are of concern as disruption of TH homeostasis may cause developmental effects in young birds.

(Table 1) Organohalogen contaminants in adipose tissue of captive sledge dogs (Canis familiaris) fed with whale blubber or pork fat

Studies on the fate of organohalogen contaminants (OHCs) in wild top predator mammals in the Arctic have often been a challenge due to important knowledge deficiencies in the life history of the sampled animals. The present study investigated the influence of age, dietary and trans-generational factors on the fate of major lipophilic chlorinated and brominated OHCs in adipose tissue of a potential surrogate captive species for the polar bear (Ursus maritimus), the sledge dog (Canis familiaris) in West Greenland. Adult female sledge dogs (P) and their sexually-mature (F1) and/or pre-weaning pups (F1-MLK) were divided into an exposed group (EXP) fed blubber from a Greenland minke whale (Balaenoptera acutorostrata) and a control group (CON) given commercially available pork fat. Large dietary treatment-related differences in summed and individual congener/compound adipose tissue concentrations of polybrominated diphenyl ethers (PBDEs), hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs) were found between the EXP and CON groups for all the sledge dog cohorts. However, among the F1-MLK, F1 and P dogs in both of the EXP and CON groups, little or no difference existed in PBDE, HCB, CHL and PCB concentrations, suggesting higher state of equilibrium in adipose tissue concentrations from a very early stage of life. In contrast, the distribution pattern (proportions to the summed concentrations) of OHC classes, and the major congeners/ compounds constituting those classes, varied on a dietary group- and/or cohort-dependent manner. The present captive sledge dog study demonstrated the importance of the confounding effects of diet composition, mother-pup association (maternal transfer), reproductive status (nursing), and to a lesser extent age in the fate of OHCs in adipose tissue of a large top carnivore mammal.

(Table S1) Brominated flame retardant concentrations in an ice core from Holtedahlfonna, Svalbard

Brominated flame retardants (BFRs) have been found in Arctic wildlife, lake sediment, and air. To identify the atmospheric BFR deposition history on Svalbard, Norway, we analyzed 19 BFRs, including hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB),and 15 polybrominated diphenyl ether congeners (PBDE) in the upper 34 m of an ice core (representing 1953-2005) from Holtedahlfonna, the western-most ice sheet on Svalbard. All of the non-PBDE compounds were detected in nearly continuous profiles in the core. Seven PBDEs were not observed above background (28,47,66,100,99,154,153), while 4 were found in 1 or 2 of 6 segments (17,85,138,183). BDEs-49,71,190,209 had nearly continuous profiles but only BDE-209 in large amounts. The greatest inputs were HBCD and BDE-209, 910, and 320 pg/cm**2/yr from 1995-2005. DBDPE, BTBPE, and PBEB show nearly continuous input growth in recent core segments, but all were <6 pg/cm**2/yr. Long-range atmospheric processes may have moved these particle-bound BFRs to the site, probably during the Arctic haze season. Average air mass trajectories over 10 years show >75% of atmospheric flow to Holtedahlfonna coming from Eurasia during haze periods (March and April).

Concentrations of brominated and chlorinated contaminants in adipose tissue of polar bears (Ursus maritimus) between 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, sum DDT (and p,p'-DDE, p,p'-DDD, p,p'-DDT) decreased (-8.4%/year); alpha-hexachlorocyclohexane (alpha-HCH) decreased (-11%/year); beta-HCH increased ( + 8.3%/year); and sum PCB and sum 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). sum chlorobenzene, octachlorostyrene, sum mirex, sum MeSO2-PCB and dieldrin did not significantly change. Increasing sum PBDE levels (+13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(alpha)-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.

(Tables S1,2) Stable isotopes in muscle tissue of polar bears (Ursus maritimus) from various regions of the Arctic

The relative contribution of regional contamination versus dietary differences to geographic variation in polar bear (Ursus maritimus) contaminant levels is unknown. Dietary variation between Alaska, Canada, East Greenland, and Svalbard subpopulations was assessed by muscle nitrogen and carbon stable isotope (d15N, d13C) and adipose fatty acid (FA) signatures relative to their main prey (ringed seals). Western and southern Hudson Bay signatures were characterized by depleted d15N and d13C, lower proportions of C20 and C22 monounsaturated FAs and higher proportions of C18 and longer chain polyunsaturated FAs. East Greenland and Svalbard signatures were reversed relative to Hudson Bay. Alaskan and Canadian Arctic signatures were intermediate. Between-subpopulation dietary differences predominated over interannual, seasonal, sex, or age variation. Among various brominated and chlorinated contaminants, diet signatures significantly explained variation in adipose levels of polybrominated diphenyl ether (PBDE) flame retardants (14-15%) and legacy PCBs (18-21%). However, dietary influence was contaminant class-specific, since only low or nonsignificant proportions of variation in organochlorine pesticide (e.g., chlordane) levels were explained by diet. Hudson Bay diet signatures were associated with lower PCB and PBDE levels, whereas East Greenland and Svalbard signatures were associated with higher levels. Understanding diet/food web factors is important to accurately interpret contaminant trends, particularly in a changing Arctic.