Paul F. Hoekstra

Biological and chemical factors of importance in the bioaccumulation and trophic transfer of persistent organochlorine contaminants in arctic marine food webs

Recent studies of arctic marine food webs have provided detailed insights regarding the biological and chemical factors that influence the bioaccumulation and trophic transfer of persistent organochlorine (OC) contaminants in aquatic systems. The present paper summarizes the recent literature with an emphasis on identifying important ecological factors for explaining variability of OC concentrations among organisms. The Arctic ecosystem has a number of unique attributes, including long food chains, reduced diversity of species, similar food webs across the entire region, and limited influence from pollution point sources. Lipid content, body size, age, gender, reproduction, habitat use, migration, biotransformation, seasonal changes in habitat conditions, feeding ecology, and trophic position have all been demonstrated to influence OC concentrations and bioaccumulation in arctic marine biota. The relative importance of each factor varies among OCs and organisms. Diet or trophic level is the dominant factor influencing OC concentrations and dynamics in seabirds and marine mammals, although biotransformation can significantly influence nonrecalcitrant OCs, such as hexachlorocyclohexane isomers. Dietary accumulation of OCs is also an important route of exposure for arctic fish and zooplankton, and biomagnification of OCs may also occur among these organisms. To date, only limited attempts have been made to model trophic transfer of OCs in the arctic marine food web. Although models developed to assess OC dynamics in aquatic food webs have included some biological variables (e.g., lipid content, feeding rate, diet composition, and growth rate), selection of processes included in these models as well as their mathematical solutions and parameterization all introduce simplification. This reduces biological validity of the models and may be particularly problematic in a highly seasonal environment, such as the Arctic Ocean.

Toxicokinetics of three polychlorinated biphenyl technical mixtures in rainbow trout (Oncorhynchus mykiss).

Accumulation and depuration parameters of polychlorinated biphenyls (PCBs) in fish have been reported only for a few congeners. As well, there is little information on the ability of fish to biotransform PCBs. To address these issues, juvenile rainbow trout (Oncorhynchus mykiss) were exposed to dietary concentrations of three Aroclor mixtures (1248, 1254, 1260) in food for 30 d followed by an additional 160 d of nonspiked food at 8 degrees C. Accumulation, depuration, and potential biotransformation of 92 PCB congeners were assessed. Half-lives (t1/2) of PCB congeners ranged from 79 to 182 d, assimilation efficiencies ranged from 40 to 50% and biomagnification factors (BMF) ranged from 2.9 to 6.9. No evidence of significant biotransformation of any PCB congeners was found. All 92 congeners fell on the same t1/2 to Kow relationship as 16 preselected PCB congeners previously shown to persist in fish and no hydroxylated PCB metabolites (OH-PCBs) were detected in the plasma after 30 d of exposure. These findings suggest that OH-PCBs observed in feral fish may be accumulated from sources other than internal metabolism of the parent congeners, at least for juvenile fish at cool temperatures. Because t1/2s in this experiment were slower than t1/2s reported in other work, water temperature also may be an important factor in determining the t1/2s of all PCB congeners in fish.

Enantiomer‐specific biomagnification of α‐Hexachlorocyclohexane and selected chiral chlordane‐related compounds within an arctic marine food web

Concentrations of achiral and chiral organochlorine contaminants (OCs), including hexachlorocyclohexane isomers (HCH), chlordane congeners (cis- and trans-chlordane, cis- and trans-nonachlor, MC5, MC7, and U82), and related metabolites (oxychlordane [OXY] and heptachlor exo-epoxide [HEPX]), were quantified in seawater (100 L; n = 6) and biota from the coastal Beaufort-Chukchi Seas food web near Barrow (AK, USA). The biota included zooplankton (Calanus spp.; n = 5), fish species such as arctic cod (Boreogadus saida; n = 10), arctic char (Salvelinus alpinus; n = 3), and marine mammals including bowhead whales (Balaena mysticetus; liver: n = 23; blubber: n = 40), beluga whales (Delphinapterus leucas; blubber: n = 20), ringed seals (Phoca hispida; blubber: n = 20), and bearded seals (Erignathus barbatus; blubber: n = 7). The food web magnification factors (FWMFs) for HCHs and chlordane compounds ranged from 0.5 (gamma-HCH) to 6.5 (HEPX) and were expected based on known recalcitrance and biotransformation of OCs. The enantiomer fractions (EFs) of all chiral OCs were near racemic (EF = 0.50) in the seawater, zooplankton, and all fish analyzed. In contrast, the EFs for most OCs analyzed were nonracemic (EF # 0.50) in the marine mammals blubber (range: 0.09-0.79) because of enantiomer-specific biotransformation and (or) accumulation. However, EF values were not significantly correlated with isotopically determined trophic level. The EFs for all chiral OCs (except alpha-HCH) in bowhead whale liver closely approximated the values in zooplankton, suggesting that the accumulation of chiral OCs from prey into this cetacean is not enantiomer specific. However, the modification of EFs from bowhead liver to blubber suggests that this species has the ability to enantioselectively biotransform and accumulate several chiral OC compounds.

Concentrations of selected essential and non-essential elements in arctic fox (Alopex lagopus) and wolverines (Gulo gulo) from the Canadian Arctic

Arctic fox (Alopex lagopus) and wolverine (Gulo gulo) tissues were collected in the Canadian Arctic from 1998 to 2001 and analyzed for various essential and non-essential elements. Several elements (Ag, Al, As, B, Ba, Be, Co, Cr, Mo, Ni, Sb, Sn, Sr, Tl, U and V) were near or below the detection limits in >95% arctic fox and wolverine samples. Concentrations of Cd, Cu, Fe, total Hg (THg), Mn, Pb, Se and Zn were quantifiable in >50% of the samples analyzed and reported herein. Hepatic elemental concentrations were not significantly different among arctic foxes collected at Ulukhaqtuuq (Holman), NT (n=13) and Arviat, NU (n=50), but were significantly greater than concentrations found in wolverine liver from Kugluktuk (Coppermine), NU (n=12). The mean (+/-1 S.E.) concentrations of Cd in kidney were also significantly greater in arctic fox (1.08+/-0.19 microg g(-1) wet wt.) than wolverine (0.67+/-0.18 microg g(-1) wet wt.). However, mean hepatic Cu concentrations (Ulukhaqtuuq: 5.5+/-0.64; Arviat: 7.1+/-0.49 microg g(-1) wet wt.) in arctic foxes were significantly lower than in wolverines (32+/-3.3 microg g(-1) wet wt.). Hepatic total Hg (THg) concentrations in arctic fox from this study were not significantly different from specimens collected in 1973, suggesting that THg concentrations have not changed dramatically over the past 30 years. The mono-methylmercury (MeHg) concentrations in selected (n=10) arctic fox liver samples from Arviat (0.14+/-0.07 microg g(-1) wet wt.) comprised 14% of THg. While the molar concentrations of THg were correlated with Se in arctic foxes and wolverines, the hepatic Hg/Se molar ratios were consistently lower than unity; suggesting that Se-mediated detoxification pathways of Hg are not overwhelmed at current exposure.

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.

Profile of persistent chlorinated contaminants, including selected chiral compounds, in wolverine (Gulo gulo) livers from the Canadian Arctic

Wolverines (Gulo gulo) are circumpolar omnivores that live throughout the alpine and arctic tundra ecosystem. Wolverine livers were collected at Kugluktuk (Coppermine), NU (n=12) in the western Canadian Arctic to report, for the first time, the residue patterns of persistent organochlorine contaminants (OCs) in this species. The enantiomer fractions (EFs) of several chiral OCs, including PCB atropisomers, in wolverines were also determined. Results were compared to OC concentrations and EFs of chiral contaminants in arctic fox (Alopex lagopus) from Ulukhaqtuuq (Holman), NT (n=20); a closely related species that scavenges the marine and terrestrial arctic environment. The rank order of hepatic concentrations for sum ( summation operator ) OC groups in wolverines were polychlorinated biphenyls ( summation operator PCB)>chlordane-related components ( summation operator CHLOR)>DDT-related compounds ( summation operator DDT)>hexachlorocyclohexane isomers ( summation operator HCHs). The most abundant OC analytes detected in wolverine liver were PCB-153, PCB-180, and oxychlordane (OXY). Wolverine age and gender did not influence OC concentrations, which were comparable to lipid-normalized values in arctic fox. The EFs of several chiral OCs (alpha-HCH, cis- and trans-chlordane, OXY, heptachlor exo-epoxide) and PCB atropisomers (PCB-136, 149) were nonracemic in arctic fox and wolverine liver and similar to those previously calculated in arctic fox and polar bears from Iceland and the Canadian Arctic. Results suggest that these species have similar ability to biotransform OCs. As well, contaminant profiles suggest that terrestrial mammals do not represent the major source of OC exposure to wolverines and that wolverines are scavenging more contaminated prey items, such as marine mammals. While summation operator PCB did not exceed the concentrations associated with mammalian reproductive impairment, future research is required to properly evaluate the potential affect of other OCs on the overall health of wolverines.

Concentrations of selected persistent organochlorine contaminants in store-bought foods from northern Alaska

Abstract Objectives. We address marine and terrestrial mammal blubber, liver, muscle, kidney, heart, tongue, maktak and maktaaq (epidermis and blubber from bowhead, beluga whales, respectively), and fish muscle and livers, as commonly consumed tissues in subsistence communities across northern Alaska in the context of organochlorine (OC) contamination of store-bought foods. Human exposure to contaminants from biota, as part of a subsistence diet, has been superficially evaluated in numerous studies (focused on liver and blubber), but are limited in the type of tissues analyzed, and rarely consider the contaminants in the alternatives (i.e., store-bought foods). Study Design. Concentrations from published literature on selected persistent organochlorine contaminants (OCs) in eight tissues of the bowhead whale and other biota (1) were compared to store-bought foods evaluated in this study. Results. As expected, store-bought foods had lower concentrations of OCs than some tissues of the marine mammals (especially blubber, maktak, and maktaaq). However, blubber is rarely eaten alone and should not be used to give consumption advice unless considered as a portion of the food item (i.e., maktak). This study indicates that the store-bought food alternatives have detectable OC concentrations (e.g., < 0.01 to 22.5 ng/g w.w. for hexachlorobenzene) and, in many cases, have greater OC concentrations than some subsistence food items. Many wildlife tissues had OC concentrations similar to those quantified in local store-bought food. Conclusions. Switching from the traditional diet to western store-bought foods will not always reduce exposure to OCs. However, raw blubber-based products are clearly more contaminated with OCs due to lipid content. A detailed profile of traditional/country foods and western foods consumed by subsistence communities of northern Alaska is required to address chronic exposure in more detail for the diverse sources of foods (subsistence use and commercially available) and the widely varying concentrations of contaminants reported therein. This should be combined with biomonitoring people dependent upon subsistence foods. Further assessment of essential and non-essential elements, emerging contaminants (e.g. brominated flame retardants), etc. should be conducted in order to improve our understanding of the differences and similarities between wildlife and store-bought foods. (Int J Circumpolar Health 2005; 64(4):303–313)