(Table 1) Lipid content and organohalogen contaminant concentration in captive sledge dogs (Canis familiaris) and wild female polar bears (Ursus maritimus) from Greenland

The limited knowledge and/or the inability to control physiological condition parameters that influence the fate of organohalogen contaminants (OHCs) has been the foremost confounding aspect in monitoring programs and health risk assessments of wild top predators in the Arctic such as the polar bear (Ursus maritimus). In the present comparative study, we used a potential surrogate Canoidea species for the East Greenland polar bear, the captive sledge dog (Canis familiaris), to investigate some factors that may influence the bioaccumulation and biotransformation of major chlorinated and brominated OHCs in adipose tissue and blood (plasma) of control (fed commercial pork fat) and exposed (fed West Greenland minke whale (Balaenoptera acutorostrata) blubber) adult female sledge dogs. Furthermore, we compared the patterns and concentrations of OHCs and their known or suggested hydroxylated (OH) metabolites (e.g., OH-PCBs) in sledge dogs with those in adipose tissue and blood (plasma) of East Greenland adult female polar bears, and blubber of their main prey species, the ringed seal (Pusa hispida). The two-year feeding regime conducted with sledge dogs led to marked differences in overall adipose tissue (and plasma) OHC residue accumulation between the control and exposed groups. Characteristic prey-to-predator OHC bioaccumulation dynamics for major PCB and PBDE congeners (patterns and concentrations) and biotransformation capacity with respect to PCB metabolite formation and OH-PCB retention distinguished, to some extent, captive sledge dogs and wild polar bears. Based on the present findings, we conclude that the use of surrogate species in toxicological investigations for species in the Canoidea family should be done with great caution, although they remain essential in the context of contaminants research with sensitive arctic top carnivore species such as the polar bear.

(Table 1) Enantiomer fractions of egg yolk and plasma samples from Svalbard glaucous gulls (Larus hyperboreus)

Glaucous gulls (Larus hyperboreus) and their eggs from Svalbard (Norwegian Arctic) have been used as biomonitors of contaminants in the marine environment. In this study, the enantiomer fractions (EFs) of chiral chlordanes and atropisomeric polychlorinated biphenyl (PCB) congeners were determined in the blood plasma of adult male and female glaucous gulls from three breeding colonies in Svalbard. Plasma EFs were similar in magnitude and direction to EFs previously reported in glaucous gulls from other arctic food webs, suggesting overall similarities in the biochemical processes influencing the EFs of bioaccumulated organochlorine (OC) contaminants within the food webs at those locations. Additionally, EFs in yolk of eggs collected concurrently from within the same nesting colonies varied with location, laying date, and OC concentrations, and may be influenced by changes in the local feeding ecology between those colonies. No differences were found between the EFs for any analyte in female gulls compared to those found in egg yolk, indicating that processes involved in the maternal transfer of chlordanes and PCBs to eggs do not modulate the stereochemical ratio between enantiomers. Therefore, the use of eggs as a valuable and noninvasive means of OC biomonitoring may also extend to enantiomer compositions in glaucous gulls, and perhaps also in other seabird species from arctic regions.

Stable isotopic ratios, shell lengths and organochlorine compounds in four bivalve species collected in July 2009 around Svalbard

Organochlorine compounds (OC) were determined in Arctic bivalves (Mya truncata, Serripes groenlan-dicus, Hiatella arctica and Chlamys islandica) from Svalbard with regard to differences in geographic location, species and variations related to their size and age. Higher chlorinated polychlorinated biphenyls (PCB 101-PCB 194), chlordanes and alpha-hexachlorocyclohexane (alpha-HCH) were consistently detected in the bivalves and PCBs dominated the OC load in the organisms. OC concentrations were highest in Mya truncata and the lowest in Serripes groenlandicus. Species-specific OC levels were likely related to differences in the species' food source, as indicated by the d13C results, rather than size and age. Higher OC concentrations were observed in bivalves from Kongsfjorden compared to the northern sampling locations Liefdefjorden and Sjuoyane. The spatial differences might be related to different water masses influencing Kongsfjorden (Atlantic) and the northern locations (Arctic), with differing phytoplankton bloom situations.

Compilation of measurements from two interdisciplinary STAR-shaped surveys in the North Sea: The ZISCH - Dataset

The measurements were obtained during two North Sea wide STAR-shaped cruises during summer 1986 and winter 1987, which were performed to investigate the circulation induced transport and biologically induced pollutant transfer within the interdisciplinary research in the project "ZISCH - Zirkulation und Schadstoffumsatz in der Nordsee / Circulation and Contaminant Fluxes in the North Sea (1984-1989)". The inventory presents parameters measured on hydrodynamics, nutrient dynamics, ecosystem dynamics and pollutant dynamics in the pelagic and benthic realm. The research program had the objective of quantifying fluxes of major budgets, especially contaminants in the North Sea. In spring 1986, following the phytoplankton spring bloom, and in late winter 1987, at minimum primary production activity, the North Sea ecosystem was investigated on a station net covering the whole North Sea. The station net was shaped like a star. Sampling started in the centre, followed by the northwest section and moving counter clockwise around the North Sea following the residual currents. By this strategy, a time series was measured in the central North Sea and more synoptic data sets were obtained in the individual sections. Generally advection processes have to be considered when comparing the data from different stations. The entire sampling period lasted for more than six weeks in each cruise. Thus, a time-lag should be considered especially when comparing the data from the eastern and the western part of the central and northern North Sea, where samples were taken at the beginning and at the end of the campaign. The ZISCH investigations represented a qualitatively and quantitatively new approach to North Sea research in several respects. (1) The first simultaneous blanket coverage of all important biological, chemical and physical parameters in the entire North Sea ecosystem; (2) the first simultaneous measurements of major contaminants (metals and organohaline compounds) in the different ecosystem compartments; (3) simultaneous determinations of atmospheric inputs of momentum, energy and matter as important ecosystem boundary conditions; (4) performance of the complex measurement program during two seasons, namely the spring plankton bloom and the subsequent winter period of minimal biological activity; and (5) support of data analysis and interpretation by oceanographic and meteorological numerical models on the same scales.

Contaminant concentrations in ivory gull (Pagophila eburnea) eggs from Svalbard and the Russian Arctic (2006-2007)

We found high levels of contaminants, in particular organochlorines, in eggs of the ivory gull Pagophila eburnea, a high Arctic seabird species threatened by climate change and contaminants. An 80% decline in the ivory gull breeding population in the Canadian Arctic the last two decades has been documented. Because of the dependence of the ivory gull on sea ice and its high trophic position, suggested environmental threats are climate change and contaminants. The present study investigated contaminant levels (organochlorines, brominated flame retardants, perfluorinated alkyl substances, and mercury) in ivory gull eggs from four colonies in the Norwegian Svalbard) and Russian Arctic (Franz Josef Land and Severnaya Zemlya). The contaminant levels presented here are among the highest reported in Arctic seabird species, and we identify this as an important stressor in a species already at risk due to environmental change.

Concentrations of persistant organic pollutants in Great skua eggs (Stercorarius skua) from Shetland 1980 and 2008

Concentrations of POPs in Great skua eggs from Shetland are among the highest in North Atlantic seabirds, with up to 11,600 µg/kg (ww) DDE and up to 17,900 µg/kg ww SumPCB. Concentrations of legacy POPs were significantly lower in 2008 than 1980. Decreases were greatest for least persistent compounds. Median SumPBDEs increased from 99 µg/kg ww in 1980 to 173 µg/kg ww in 2008. There were changes in Great skua breeding season diet, with more adult Herring and Mackerel and less Sandeel. These changes increase exposure to POPs, since Herring and Mackerel accumulate more POPs than Sandeels. In both years, eggs with higher d15N had higher POP concentrations. In 1980, birds feeding more on demersal discard fish from trawl fisheries and less on Sandeels, had higher POP levels in eggs. In 2008, individuals feeding more on Herring and Mackerel, and less on discards, had higher POP levels in eggs.

(Table 1) Circulating levels of TT3 and TT4, and age, length, girth, and estimated body mass in polar bears (Ursus maritimus) from East Greenland 1999-2001

We investigated the multivariate relationships between adipose tissue residue levels of 48 individual organohalogen contaminants (OHCs) and circulating thyroid hormone (TH) levels in polar bears (Ursus maritimus) from East Greenland (1999-2001, n = 62), using projection to latent structure (PLS) regression for four groupings of polar bears; subadults (SubA), adult females with cubs (AdF_N), adult females without cubs (AdF_S) and adult males (AdM). In the resulting significant PLS models for SubA, AdF_N and AdF_S, some OHCs were especially important in explaining variations in circulating TH levels: polybrominated diphenylether (PBDE)-99, PBDE-100, PBDE-153, polychlorinated biphenyl (PCB)-52, PCB-118, cis-nonachlor, trans-nonachlor, trichlorobenzene (TCB) and pentachlorobenzene (QCB), and both negative and positive relationships with THs were found. In addition, the models revealed that DDTs had a positive influence on total 3,5,3'-triiodothyronine (TT3) in AdF_S, and that a group of 17 higher chlorinated ortho-PCBs had a positive influence on total 3,5,3',5'-tetraiodothyronine (thyroxine, TT4) in AdF_N. TH levels in AdM seemed less influenced by OHCs because of non-significant PLS models. TH levels were also influenced by biological factors such as age, sex, body size, lipid content of adipose tissue and sampling date. When controlling for biological variables, the major relationships from the PLS models for SubA, AdF_N and AdF_S were found significant in partial correlations. The most important OHCs that influenced TH levels in the significant PLS models may potentially act through similar mechanisms on the hypothalamic-pituitary-thyroid (HPT) axis, suggesting that both combined effects by dose and response addition and perhaps synergistic potentiation may be a possibility in these polar bears. Statistical associations are not evidence per se of biological cause-effect relationships. Still, the results of the present study indicate that OHCs may affect circulating TH levels in East Greenland polar bears, adding to the "weight of evidence" suggesting that OHCs might interfere with thyroid homeostasis in polar bears.

Concentration of persistant organic pollutants and mercury in seabird eggs collected in Norway

The main objective of this study was to investigate possible temporal trends of persistent organic pollutants (POPs) and mercury in eggs of herring gulls (Larus argentatus), black-legged kittiwakes (Rissa tridactyla), common guillemots (Uria aalge) and Atlantic puffins (Fratercula arctica) in Northern Norway. Eggs were collected in 1983, 1993 and 2003. Egg concentrations of POPs (PCB congeners IUPAC numbers: CB-28, 74, 66, 101, 99, 110, 149, 118, 153, 105, 141, 138, 187, 128, 156, 157, 180, 170, 194, 206, HCB, alph-HCH, beta-HCH, gamma-HCH, oxychlordane, trans-chlordane, cis-chlordane, trans-nonachlor, cis-nonachlor, p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT and p,p'-DDT) and mercury were quantified. Generally, POP levels decreased between 1983 and 2003 in all species. No significant temporal trend in mercury levels was found between 1983 and 2003.

(Table 1) Concentration of pollutants in hair of East Greenland polar bears (Ursus maritimus)

Hair sampled from 96 East Greenland polar bears (Ursus maritimus) over the periods 1892-1927 and 1988-2009 was analyzed for cortisol as a proxy to investigate temporal patterns of environmental stress. Cortisol concentration was independent of sex and age, and was found at significantly higher (p<0.001) concentrations in historical hair samples (1892-1927; n = 8) relative to recent ones (1988-2009; n = 88). In addition, there was a linear time trend in cortisol concentration of the recent samples (p< 0.01), with an annual decrease of 2.7%. The recent hair samples were also analyzed for major bioaccumulative, persistent organic pollutants (POPs). There were no obvious POP related time trends or correlations between hair cortisol and hair POP concentrations. Thus, polar bear hair appears to be a relatively poor indicator of the animal's general POP load in adipose tissue. However, further investigations are warranted to explore the reasons for the temporal decrease found in the bears' hair cortisol levels.

(Table 2) Organochlorine concentrations in polar bears (Ursus maritimus) from East Greenland 1999-2001

Persistent organochlorine (OC) contaminants (PCBs, DDTs, chlordanes (CHLs), dieldrin, hexachlorocyclohexanes (HCHs), chlorobenzenes (CBzs)) were determined in adipose tissue of 92 polar bears (Ursus maritimus) sampled between 1999 and 2001 in central East Greenland (69°00'N to 74°00'N). OC data were presented from subadults (S: females: <5 years and males: <6 years), adult females (F: >=5 years) and adult males (M: >=6 years). Summed chlorobiphenyl (SumCBs) concentrations (41 congeners including co-eluters), SumCHLs and SumDDTs were the dominant classes of OCs. SumCBs concentrations were found to be 6470, 8240 and 9100 ng/g lipid weight (lw) i subadults, adult females and adult males, respectively. The corresponding figures were: 2010 (S), 2220 (F) and 1710 (M) ng/ g lw for SumCHLs and 462 (S), 462 (F) and 559 (M) ng/g lw for SumDDTs. The dominant CB congeners were CB153 (32.3%), CB180 (21.4%), CB170 (12.2%) and CB138 (11.0%). The metabolite p,p'-DDE (88.2%) dominated the SumDDTs, while oxychlordane was the dominant (57.1%) CHL-related compound. Concentrations of SumCBs, SumCBzs, SumDDTs, mirex and dieldrin were highest in adult males, whereas concentrations of SumHCHs were lower than in adult females but not than those in subadults. Adult females had the lowest concentrations of SumCBzs, mirex and dieldrin. Concentrations of SumCHLs were lowest in adult males, intermediate in subadults and highest in adult females. SumCB, SumHCH and SumCHL concentrations showed high seasonal variability in adult females but remained relatively constant in adult males and subadults. In general, the OC levels in females appeared to be highest in March and lowest in January or September. Concentrations of SumCBzs and dieldrin showed seasonal variability in all three groups, with a maximum in March in adult females. SumCBz concentrations in adult males and subadults of both sexes peaked in April-July, and dieldrin concentrations peaked in April-July in subadults, but not until August in adult males. SumDDT concentrations increased from January to a maximum in April-July for subadults and in August for adults. Temporal trends within the last decade were examined by comparing the present data to the concentrations reported in samples from 1990 from the same region. SumCB, p,p'-DDE and SumHCH concentrations in 1999-2001 were 22.1%, 66.3% and 39.3% lower than the 1990 concentrations, respectively. in contrast, SumCHL and dieldrin concentrations showed differences amongst sex and age groups in the temporal trends, where present concentrations are between 24.4% to 69.3% and 27.0% to 69.0% lower, respectively, relative to the 1990 levels. However, power analysis suggested that firm conclusions could not be drawn regarding the general time trend based on these two sampling periods. The range of half-lives of the various OC classes were estimated to lie between 4.5 and 20.6 years depending on the age and sex groups considered.

(Table 1) Concentration of organohalogenated compounds in clean and contaminated hair of polar bears (Ursus maritimus) from East Greenland

In this pilot study, we report on levels of persistent organohalogenated contaminants (OHCs) in hair of polar bears (Ursus maritimus) from East Greenland sampled between 1999 and 2001. To our knowledge, this is the first study on the validation of polar bear hair as a non-invasive matrix representative of concentrations and profiles in internal organs and blood plasma. Because of low sample weights (13-140 mg), only major bioaccumulative OHCs were detected above the limit of quantification: five polychlorinated biphenyl (PCB) congeners (CB 99, 138, 153, 170 and 180), one polybrominated diphenyl ether (PBDE) congener (BDE 47), oxychlordane, trans-nonachlor and ß-hexachlorocyclohexane. The PCB profile in hair was similar to that of internal tissues (i.e. adipose, liver, brain and blood), with CB 153 and 180 as the major congeners in all matrices. A gender difference was found for concentrations in hair relative to concentrations in internal tissues. Females (n = 6) were found to display negative correlations, while males (n = 5) showed positive correlations, although p-values were not found significant. These negative correlations in females may reflect seasonal OHC mobilisation from periphery adipose tissue due to, for example, lactation and fasting. The lack of significance in most correlations may be due to small sample sizes and seasonal variability of concentrations in soft tissues. Further research with larger sample weights and sizes is therefore necessary to draw more definitive conclusions on the usefulness of hair for biomonitoring OHCs in polar bears and other fur mammals.

Enzyme activity and liver tissue PCB concentrations of chicks of northern fulmars (F. glacialis) and black-legged kittiwakes (R. tridactyla) from Kongsfjorden

Arctic seabirds are exposed to a wide range of halogenated organic contaminants (HOCs). Exposure occurs mainly through food intake, and many pollutants accumulate in lipid-rich tissues. Little is known about how HOCs are biotransformed in arctic seabirds. In this study, we characterized biotransformation enzymes in chicks of northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla) from Kongsfjorden (Svalbard, Norway). Phase I and II enzymes were analyzed at the transcriptional, translational and activity levels. For gene expression patterns, quantitative polymerase chain reactions (qPCR), using gene-sequence primers, were performed. Protein levels were analyzed using immunochemical assays of western blot with commercially available antibodies. Liver samples were analyzed for phase I and II enzyme activities using a variety of substrates including ethoxyresorufin (cytochrome (CYP)1A1/1A2), pentoxyresorufin (CYP2B), methoxyresorufin (CYP1A), benzyloxyresorufin (CYP3A), testosterone (CYP3A/CYP2B), 1-chloro-2,4-nitrobenzene (CDNB) (glutathione S-transferase (GST)) and 4-nitrophenol (uridine diphosphate glucuronyltransferase (UDPGT)). In addition, the hydroxylated (OH-) polychlorinated biphenyls (PCBs) were analyzed in the blood, liver and brain tissue, whereas the methylsulfone (MeSO2-) PCBs were analyzed in liver tissue. Results indicated the presence of phase I (CYP1A4/CYP1A5, CYP2B, and CYP3A) and phase II (GST and UDPGT) enzymes at the activity, protein and/or mRNA level in both species. Northern fulmar chicks had higher enzyme activity than black-legged kittiwake chicks. This in combination with the higher XOH-PCB to parent PCB ratios suggests that northern fulmar chicks have a different biotransformation capacity than black-legged kittiwake chicks.