Contaminant residues in seabird eggs from the Canadian Arctic. Part I. Temporal trends 1975-1998.

Concentrations of total mercury, selenium and a suite of organochlorine compounds were measured in eggs of thick-billed murres (Uria lomvia), northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla) collected on Prince Leopold Island in Lancaster Sound, Nunavut, Canada, between 1975 and 1998. Mercury levels in thick-billed murre and northern fulmar eggs increased significantly during this period while selenium concentrations decreased significantly in northern fulmar eggs. Mercury and selenium concentrations in black-legged kittiwake eggs exhibited no significant temporal trends. Concentrations of sigma PCB, sigma DDT and total chlorobenzenes decreased over time for all three species and there was a shift in the PCB congener pattern as the hexachlorobiphenyl fraction of sigma PCB increased and the lower chlorinated biphenyl fraction decreased. Total chlordane, dieldrin and mirex concentrations decreased in kittiwake eggs while no significant trends were observed for the other two species. Increases in sigma HCH levels were detected in thick-billed murre eggs but not in northern fulmar and black-legged kittiwake eggs. Levels of the beta-HCH isomer, however, increased significantly in murres and fulmars. Stable-nitrogen isotope analyses (delta 15N) indicate that the temporal trends observed for contaminant concentrations in eggs were not the result of shifts in trophic level. Changing deposition patterns of xenobiotic compounds over the summer and winter ranges of these birds provide a likely explanation for differing exposures through time.     

Temporal trends of organochlorines and mercury in seabird eggs from the Canadian Arctic, 1975-2003

Organochlorine pesticides, PCBs, total mercury and selenium were measured in eggs of thick-billed murres, northern fulmars and black-legged kittiwakes collected from Prince Leopold Island in the Canadian High Arctic between 1975 and 2003. The primary organochlorines found were SigmaPCB, p,p'-DDE, oxychlordane, and hexachlorobenzene (HCB). Most of organochlorines analyzed showed either significant declines or no significant change between 1975 and 2003 in all three species. However, significant increases were observed for SigmaHCH in the kittiwakes and fulmars, and beta-HCH in the murres and fulmars. Mercury increased significantly in eggs of murres and fulmars, whereas mercury in the kittiwakes did not change significantly over the study period. Statistical analyses included stable-nitrogen isotope ratios (delta(15)N) to control for any variation in trophic level over time. Although the contaminant concentrations reported in this study are below published threshold values, mercury and beta-HCH concentrations continue to increase suggesting that continued monitoring is warranted.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

Dioxins, PCBs, and HCB in soil and peat profiles from a pristine boreal catchment

The aim of this study was to explore how atmospherically derived soil pollution is affected by environmental processes at two typical boreal catchment landscape type settings: wetlands and forested areas. Measurements of hydrophobic organic compounds (HOCs) in forest soil and peat from an oligotrophic mire at various depths were performed at a remote boreal catchment in northern Sweden. HOCs in peat were evenly distributed throughout the body of the mire while levels of HOCs in the forest soil increased with increased amount of organic matter. Evaluation of HOC composition by principal component analysis (PCA) showed distinct differences between surface soils and deeper soil and peat samples. This was attributed to vertical transport, degradation and/or shifting sources over time. The calculated net vertical transport differed between surface layers (0.3%) and deeper soils (8.0%), suggesting that vertical transport conditions and processes differ in the deeper layers compared to the surface layers.     

Modelling the fate of hydrophobic organic contaminants in a boreal forest catchment: A cross disciplinary approach to assessing diffuse pollution to surface waters

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day⁻¹ during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons.     

Organochlorine contaminant and stable isotope profiles in Arctic fox (Alopex lagopus) from the Alaskan and Canadian Arctic

Arctic fox (Alopex lagopus) is a circumpolar species distributed across northern Canada and Alaska. Arctic fox muscle and liver were collected at Barrow, AK, USA (n=18), Holman, NT, Canada (n=20), and Arviat, NU, Canada (n=20) to elucidate the feeding ecology of this species and relate these findings to body residue patterns of organochlorine contaminants (OCs). Stable carbon (delta 13C) and nitrogen (delta 15N) isotope analyses of Arctic fox muscle indicated that trophic position (estimated by delta 15N) is positively correlated with increasing delta 13C values, suggesting that Arctic fox with a predominantly marine-based foraging strategy occupy a higher trophic level than individuals mostly feeding from a terrestrial-based carbon source. At all sites, the rank order for OC groups in muscle was polychlorinated biphenyls (Sigma PCB) > chlordane-related compounds (Sigma CHLOR) > hexachlorocyclohexane (Sigma HCH) > total toxaphene (TOX) > or = chlorobenzenes (Sigma ClBz) > DDT-related isomers (Sigma DDT). In liver, Sigma CHLOR was the most abundant OC group, followed by Sigma PCB > TOX > Sigma HCH > Sigma ClBz > Sigma DDT. The most abundant OC analytes detected from Arctic fox muscle and liver were oxychlordane, PCB-153, and PCB-180. The comparison of delta 15N with OC concentrations indicated that relative trophic position might not accurately predict OC bioaccumulation in Arctic fox. The bioaccumulation pattern of OCs in the Arctic fox is similar to the polar bear. While Sigma PCB concentrations were highly variable, concentrations in the Arctic fox were generally below those associated with the toxicological endpoints for adverse effects on mammalian reproduction. Further research is required to properly elucidate the potential health impacts to this species from exposure to OCs.     

Stable isotope determination in wild and farmed gilthead sea bream (Sparus aurata) tissues from the western Mediterranean

Stable isotopes of carbon and nitrogen (delta(13)C and delta(15)N) have been determined in wild and farmed gilthead sea bream (Sparus aurata) samples of white and red muscle, liver, gills and gonads. First, delta(13)C and delta(15)N values were determined in samples with and without lipid removal to check the possible effect of lipid content on the stable isotope values of the different tissues studied. Differences were found for delta(13)C in all tissues studied apart from white muscle of wild fish, the tissue with the lowest lipid content. For delta(15)N values no differences were found in wild fish tissues. Liver from farmed fish showed lower delta(15)N value after lipid removing. Further conclusions were based on results obtained from lipid-free samples. delta(13)C of cultured fish tissues showed a mean depletion of 2.9+/-0.4 per thousand compared to wild specimens, suggesting different sources of carbon in the diet, probably due to the feed used during sea-cage culture. Cultured gilthead sea bream tissues were significantly more enriched in nitrogen than wild specimens by an average of 1.5+/-0.2 per thousand in white muscle, indicating a slight increase in the trophic level. Determination of stable isotope signatures of gilthead sea bream tissues allows clear discrimination between wild and cultured sea bream, and characterisation of differences in diet and feeding conditions in any tissue studied.     

Trace metal and stable isotope measurements (delta13C and delta15N) in the harbour porpoise Phocoena phocoena relicta from the Black Sea

Stable carbon and nitrogen isotopes (delta13C and delta15N) and trace metals (Cd, Zn, Cu, Fe, Se, and Hg) were analysed in the tissues of 46 harbour porpoises (Phocoena phocoena relicta) caught in fishing nets along the Ukrainian coasts between 1997 and 1998. Mean delta13C values differed significantly between male and female harbour porpoises suggesting a trophic segregation between sexes with a more coastal distribution for females at least during their gestation and nursing periods. Hepatic Hg was correlated to delta13C measurements, reflecting a different exposure linked to coastal vs offshore feeding habitats. A geographical comparison with existing data from other regions showed general low levels of Hg, Cd, Cu and Zn in the tissues of harbour porpoises from the Black Sea compared to other Atlantic and North Sea areas.     

Regional patterns in foliar (15)N across a gradient of nitrogen deposition in the northeastern US

Recent studies have demonstrated that natural abundance (15)N can be a useful tool for assessing nitrogen saturation, because as nitrification and nitrate loss increase, delta(15)N of foliage and soil also increases. We measured foliar delta(15)N at 11 high-elevation spruce-fir stands along an N deposition gradient in 1987-1988 and at seven paired northern hardwood and spruce-fir stands in 1999. In 1999, foliar delta(15)N increased from -5.2 to -0.7 per thousand with increasing N deposition from Maine to NY. Foliar delta(15)N decreased between 1987-1988 and 1999, while foliar %N increased and foliar C:N decreased at most sites. Foliar delta(15)N was strongly correlated with N deposition, and was also positively correlated with net nitrification potential and negatively correlated with soil C:N ratio. Although the increase in foliar %N is consistent with a progression towards N saturation, other results of this study suggest that, in 1999, these stands were further from N saturation than in 1987-1988.     

Carbon and nitrogen composition and stable isotope as potential indicators of source and fate of organic matter in the salt marsh of the Changjiang Estuary, China

Elemental (TOC, TN, C/N) and stable carbon and nitrogen isotopic (delta(13)C, delta(15)N) compositions were measured for surface sediments, three sediment vibrocores, plants, and suspended particulate matter (SPM) collected from salt marsh of the Changjiang Estuary. The purpose of this study is to characterize the sources of organic matter in sediments and to further elucidate the factors influencing the isotope signature in the salt marsh. Our results indicate that organic matter preserved in the sediments is predominantly controlled by the particulate organic matter in the Changjiang Estuary. The in situ contribution of marsh plants carbon to sediment organic matter is clearest in the high marsh, where the low delta(13)C of the plants (-28.1 per thousand) is reflected by a sediment delta(13)C (-24.7 per thousand) lower than values found for the low marsh and bare flat sediments (-23.4 per thousand and -23.0 per thousand, respectively). The effect of grain size on the spatial difference of isotope composition in the marsh sediments is insignificant, based on the observation that similar isotope values are found in different size particles, both for delta(13)C and delta(15)N. Nutrient utilization by plant assimilation, however, shows great impact on the surface sediment delta(15)N composition, due to the isotope fractionation. With extensive plant coverage and the consequent low surface water nitrate concentration, delta(15)N values of the high marsh surface sediments show (15)N enrichment.     

The use of sedimentary %C, %N, delta(15)N, and Pb concentrations to assess historical changes in anthropogenic influence on Portuguese estuaries

Vertical profiles of C, N, delta(15)N and Pb were measured in the Mondego and Mira estuaries as markers that conveyed notions as to the relative influence of anthropogenic influence over the past decades. Recent carbon changes in both estuaries may reflect changes in estuarine productivity, probably as a consequence of sediment reworking and erosion, and also of losses in salt marsh area and dwarf eelgrass beds. delta(15)N values began to diverge considerably before the %C and %N and were higher in Mondego. delta(15)N signatures detected N enrichment at relatively low rates, and indicated that Mondego received more enriched N than Mira. Lead concentrations differed between estuaries, with higher concentrations in Mondego. The secular increase in %N, Pb, and delta(15)N signatures was significantly related to human density in the watersheds of the estuaries and were sensitive indicators of anthropogenic activity.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.     

Congener-specific accumulation and trophic transfer of polychlorinated biphenyls in spider crab food webs revealed by stable isotope analysis

Polychlorobiphenyls (PCB) and stable isotopes (delta15N and delta13C) were analyzed in the spider crab (Maja brachydactyla) food web from the Iroise Sea (Western Brittany) and the Seine Bay (Eastern English Channel). PCB concentrations were all significantly higher in organisms from the Seine Bay than those from the Iroise Sea. PCB patterns were strongly related to the feeding mode of the species, and increased influence of higher chlorinated congeners was highlighted with trophic position of the organisms. PCB concentrations (lipid normalized) were significantly related to the isotopically derived trophic level (TL) in spider crab food webs. The highest trophic magnification factors (TMFs) were calculated for the congeners with 2,4,5-substitution, and were lower in the Seine Bay compared to the Iroise Sea. The confrontation of PCB and TL data also revealed biotransformation capacity of decapod crustaceans for specific congeners based on structure-activity relations.     

Organochlorine contaminants in seven species of Arctic seabirds from northern Baffin Bay

Organochlorine contaminants (OCs) were determined in liver and fat of seven species of seabirds (Alle alle, Uria lomvia, Cepphus grylle, Rissa tridactyla, Pagophila eburnea, Larus hyperboreus, and Fulmaris glacialis) collected in May/June 1998 from the Northwater Polynya in northern Baffin Bay. OC concentrations ranged over an order of magnitude between seabird species and OC groups, with PCBs having the highest concentrations followed by DDT, chlordane, HCH and ClBz. Positive relationships between delta15N (estimator of trophic level) and OC concentrations (lipid basis) were found for all OC groups, showing that trophic position and biomagnification significantly influence OC concentrations in Arctic seabirds. Concentrations of a number of OCs in particular species (e.g., HCH in P. eburnean) were lower than expected based on delta15N and was attributed to biotransformation. P. eburnea and F. glacialis, which scavenge, and R. tridactyla, which migrate from the south, were consistently above the delta15N-OC regression providing evidence that these variables can elevate OC concentrations. Stable isotope measurements in muscle may not be suitable for identifying past scavenging events by seabirds. OC relative proportions were related to trophic position and phylogeny, showing that OC biotransformation varies between seabird groups. Trophic level, migration, scavenging and biotransformation all play important roles in the OCs found in Arctic seabirds.     

Bioaccumulation of PCBs in Arctic seabirds: influence of dietary exposure and congener biotransformation

Four seabird species and their prey (zooplankton or fish) were collected in the Barents Sea to determine how dietary exposure, cytochrome P450 (CYP) enzyme activities and sex influenced their hepatic PCB concentrations and accumulation patterns. Five males and five females from each seabird species (little auk (Alle alle), Brunnich's guillemot (Uria lomvia), black guillemot (Cepphus grylle) and black-legged kittiwake (Rissa tridactyla)) were analysed. PCB concentrations could not be explained directly by carbon source (delta13C) or trophic position (delta15N), but by a combination of dietary parameters (delta13C, delta15N, migratory pattern, age) and contaminant metabolism. Contrary to previous studies, the PCB pattern differed among seabirds, with a higher proportion of persistent congeners (% of PCB-153, RPCB-153) in black-legged kittiwake than in auks. The PCB pattern also differed among auks, with little auk as the most efficient biotransformer (highest RPCB-153 values of persistent congeners). Based on high RPCB-153 values, Brunnich's guillemot poorly metabolised ortho-meta-unsubstituted congeners, whereas black guillemot poorly metabolised meta-para unsubstituted congeners. Species-specific differences in PCB biotransformation were confirmed by metabolic indices, where PCB patterns in seabirds were adjusted for PCB pattern in prey. The relative contribution of ortho-meta-unsubstituted congeners to SigmaPCBs decreased with increasing EROD activity. There were no differences in PCB concentrations, PCB patterns or cytochrome P450 enzyme activities between males and females. CYP P450 activities (CYP1A- and CYP2B/3A-like: EROD and testosterone 6beta-hydroxylation, respectively) were low and did not correlate with concentrations of non- or mono-ortho Cl-substituted PCBs (NO- and MO-PCBs), or with total toxic equivalent concentrations (TEQs) for dioxin-like effects of NO- and MO-PCBs.     

Biomarker responses associated with halogenated organic contaminants in northern fulmars (Fulmarus glacialis) breeding in the Canadian Arctic

We examined relationships between hepatic concentrations of halogenated organic contaminants and ethoxyresorufin O-deethylase (EROD) activity and retinoid (vitamin A) concentrations in livers, as well as retinol and thyroid hormone (TT₃, TT₄) levels in blood plasma, of northern fulmars at two breeding colonies in the Canadian High Arctic. Biomarker levels or responses did not differ significantly between males and females at either colony, nor was there any significant difference between colonies. No significant relationships were found between thyroid hormone or hepatic retinoid concentrations and any of the dioxin-like compounds or their Toxic Equivalents (TEQs) although significant positive correlations were found with plasma retinol (p < 0.03). EROD activity was significantly correlated with hepatic dioxin-like compounds and their TEQs (p < 0.001) as well as total PCBs (p < 0.01), which suggests that EROD induction occurs in northern fulmars at environmentally-relevant concentrations.     

Levels and distribution of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in sediments and biota from the Danube Delta, Romania

Concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), such as dichlorodiphenyltrichloroethane (DDT) and analogues, hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB), were measured in sediments and biota (invertebrates, 11 fish species and cormorant tissues) collected in 2001 from the Danube Delta, the biggest European wetland. DDTs were the predominant pollutants in all samples. A high variability in the concentrations of pollutants within the same species was observed and this was related to sampling location, age, length and sex. DDTs were also the main organohalogenated contaminants in cormorant muscle and liver, followed by PCBs, HCHs, HCB and PBDEs. The present levels of DDTs in cormorant tissues are lower than levels measured in cormorant eggs sampled from the Danube Delta in 1982 and 1997, respectively. The variance of delta15N for herbivores was much greater than for carnivores, while carp and bream showed higher delta15N signatures than expected, probably due to a higher dietary proportion of benthos, typically more delta15N enriched relative to pelagic biota.     

Use of carbon and nitrogen stable isotope ratios to assess the effects of environmental contaminants on aquatic food webs

In this study, the value of carbon (delta13C) and nitrogen (delta15N) stable isotope ratios were determined in nymphs of a top-predator, the common backswimmer (Notonecta glauca L.), collected in 18 m3 outdoor freshwater mesocosms used to assess the fate and ecotoxicological effects of a diphenyl ether herbicide, fomesafen, applied alone or in combination with Agral 90 (mixture of polyethoxylated derivatives of nonylphenol). Both treatments had a negative effect on delta13C values which may reflect changes in carbon fluxes across food webs in the treated ponds associated with a shift in phytoplankton structure. A decrease in delta15N values was observed in the nymphs collected in mixture-treated ponds, which was presumably due to an increase in the abundance of rotifers and Chironominae larvae in these ponds. These preliminary results indicate that stable isotope ratios may be used as shortcuts to detect qualitative or quantitative shifts in the structure of aquatic food webs caused by pollutants.     

Sorption of hydrophobic organic compounds onto organoclays

The behavior and fate of nonionic hydrophobic organic compounds (HOCs) in the environment are mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of the contaminants in the environment. In our experiments, HOC sorption by hexadecyltrimethylammonium (HDTMA)-modified smectite linearly increased with the amount of HDTMA added to the clay. However, tetramethylammonium (TMA)- and dodecyltrimethylammonium (DTMA)-modified smectites showed not only inferiority in their sorption of HOC compared with the HDTMA-smectite, but also a partially decreased HOC sorption at specific surfactant loading levels. This means that the sorption of organoclays for organic contaminants was significantly influenced by the amount and size of the surfactants added on the clay. In addition, it seems that the interlayer structure (e.g., pore size) formed at each surfactant loading level plays an important role to adsorb HOC in different amount.