Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003.

Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from < 0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2',4,4'-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from < 0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1'-dimethyl-tetrabromo-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2',4,4'-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.

Elemental composition of liver and kidney tissues of rough-toothed dolphins (Steno bredanensis).

On December 14, 1997, 62 rough-toothed dolphins (Steno bredanensis) stranded on Cape San Blas, on the Florida coast of the Gulf of Mexico. Approximately 30 animals died either on the beach or in rehabilitation facilities. Two were successfully rehabilitated and released. Liver, kidney, blubber, and muscle tissues were collected from 15 animals that died on the beach. Portions of the liver and kidney from each dolphin were analyzed using instrumental neutron activation analysis and inductively coupled plasma mass spectrometry to determine mass fractions of 37 elements. Levels of several electrolytes (Na, Cl, K, Br, Rb, I, Cs) and of the essential trace elements Fe, Cu, and Zn in both tissues were similar to those found in other Odontoceti. Mass fractions of Ca ranged from 60 mg/kg to 1,200 mg/kg (wet mass basis), indicating significant inhomogeneity in the kidney tissues of several animals. Necropsy reports noted that the kidneys of many of these animals contained fibrous nodules. The measured Ca inhomogeneity may be due to mineralization of the fibrous kidney tissue. Hepatic levels of Hg and Se were at the high end of the ranges generally found in livers of other Odontoceti and were slightly higher in animals with fibrous kidneys than in the others. Mass fractions of Se, Ag, and Hg in liver tissues increased with the size and age of the animals indicating accumulation of these elements in the liver with age. Results also indicate that Se and Hg accumulate in rough-toothed dolphin kidney. Accumulation of these elements with age has been reported commonly for marine mammals and other species.

Organochlorine contaminant levels in Eskimo harvested bowhead whales of arctic Alaska.

Organochlorine (OC) levels in liver and blubber of 20 bowhead whales (Balaena mysticetus) collected during the Eskimo subsistence harvest at Barrow (Alaska, USA) in 1992 and 1993 are presented. Liver sum DDT (lipid weight) was significantly greater in male whales than in females. Most of the organochlorines measured were at higher levels in longer (older) than in shorter (younger) males. For female bowhead whales, hexachlorobenzene and lipid levels decreased and other OC levels did not change significantly with increasing length. Most organochlorine contaminants have low concentrations in tissues of the bowhead whale compared to concentrations in tissues of other cetaceans, especially Odontocetes. Based on allowable daily intakes (ADI) levels established by the Canadian Northern Contaminants Program (Ottawa, Ontario, Canada) "safe" levels of blubber to consume were calculated. Chlordane levels in bowhead whale blubber results in the most restrictive consumption amount (50 g blubber/day). We expect no adverse effects related to these organochlorine contaminants to occur in bowhead whales or in consumers of their tissues. However, investigation of low level chronic exposure effects and a more rigorous assessment of histopathology, biomarkers, and immune status in the bowhead whale would be required to conclude "no effect" with more certainty.

Quality assurance in analysis of cryogenically stored liver tissue specimens from the NIST National Biomonitoring Specimen Bank (NBSB).

Portions of liver tissue specimens originally stored in the National Biomonitoring Specimen Bank (NBSB) and analyzed between 1980 and 1987 were re-analyzed in 1997 using instrumental neutron activation analysis (INAA) for the determination of 17 trace elements. Duplicate portions of each specimen had been stored at two different temperatures. The first was stored in a liquid nitrogen vapor-cooled freezer at -150 degrees C, standard NBSB storage conditions, and the other in an electric freezer maintained at -80 degrees C. Two portions of seven livers from each storage temperature were re-analyzed for this work. Results showed no changes in trace element content as a function of storage temperature, within the uncertainty of the method used. Results from these analyses agreed with results of initial analyses for most analytes in most sub-samples. Of the exceptions, five were due, in part, to an incorrect basis mass for the initial sub-specimen of one tissue, five with variable Zn results were attributed to difficulties in peak fitting for this element during INAA data processing, and the remaining were isolated differences discussed in this paper. Results of this work indicate that specimen storage and processing protocols are adequate to prevent noticeable contamination of specimens with trace elements, with the exception of Cr. Variability in Cr content was observed for the liver tissues which may have been caused by Cr contamination of the samples by the Teflon mill. Analyses of portions of Standard Reference Material (SRM) 1566a Oyster Tissue (certified in 1989) and SRM 1577a Bovine Liver (certified in 1982) were also included in this study for the purpose of quality control and to assess the stability of these freeze-dried powders that were stored at room temperature. No changes were observed in these materials.

Twenty years of trace metal analyses of marine mammals in Alaska: evaluation and summation.

The compilation of existing data on contaminants in the marine food chain is essential in addressing concerns regarding the magnitude of potential human exposures and in the evaluation of subsistence food safety. This paper presents a summary of studies on trace metals in tissues of Alaska marine mammals from the 1970s to the present, along with derived mean tissue trace metal concentrations. The derived mean can serve as a norm against which future monitoring results may be compared, and may be used to estimate human exposure to trace metals through the consumption of marine mammals. Additionally, the variation among studies in the reported mean tissue concentrations has been described through a derived standard deviation. Sufficient analytical and methodological details were available to derive means and standard deviations for tissues in bearded seal, bowhead whale, beluga whale, fur seal, harbor seal, Pacific walrus, and ringed seal. A high concordance between trace metal values reported in tissues (i.e., liver, kidney, muscle) was observed despite significant differences in reported sampling and analytical methodologies. Consistent with other reviews of trace metal concentrations in marine species, the standard deviation of tissue metal concentrations was generally < or = 100% of the reported mean. Significant gaps in available information remain, particularly for muscle tissues and for methylmercury, despite the considerable efforts to monitor marine mammal species in Alaska.

Specimen banking of marine organisms in the United States: current status and long-term prospective.

A major part of the activities conducted over the last decade by the National Biomonitoring Specimen Bank (NBSB) has involved the archival of marine specimens collected by ongoing environmental monitoring programs. These archived specimens include bivalves, marine sediments, and fish tissues collected by the National Status and Trends and the Exxon Valdez Oil Spill Damage Assessment programs, and marine mammal tissues collected by the Marine Mammal Health and Stranding, Response Program and the Alaska Marine Mammal Tissue Archival Project. In addition to supporting these programs, the specimens have been used to investigate circumpolar patterns of chlorinated hydrocarbon concentrations, genetic separation of marine animal stocks, baseline levels of essential and nonessential elements in marine mammals, and the potential risk to human consumers in the Arctic from anthropogenic contaminants found in local subsistence foods. The NBSB specimens represent a resource that has the potential for addressing future issues of marine environmental quality and ecosystem changes through retrospective analysis; however, an ecosystem-based food web approach would maximize this potential. The current status of the NBSB activities related to the banking of marine organisms is presented and discussed, the long-term prospective of these activities is presented, and the importance of an ecosystem-based food web monitoring approach to the value of specimen banking is discussed.

Concentrations of chlorinated hydrocarbons and trace elements in marine mammal tissues archived in the U.S. National Biomonitoring Specimen Bank.

The U.S. National Biomonitoring Specimen Bank (NBSB) provides for the long term storage of well documented and preserved specimens representing several types of environmental matrices. A major part of this inventory consists of marine mammal tissues (e.g., blubber, liver, kidney, and muscle). Within the NBSB selected specimens are periodically analyzed for chlorinated hydrocarbons and trace elements. Although only 20% of the 560 marine mammal specimens in the NBSB have been analyzed, the database is of value in evaluating the stability of analytes and sample degradation during storage, for comparing with results from samples collected in the future for long-term monitoring, and for comparing with analytical results from other laboratories on samples collected at the same time for monitoring purposes. The NBSB analytical database contains results for 37 elements, many of which are not analyzed routinely by conventional analytical techniques used in monitoring programs, and the following organic compounds: selected PCB congeners. DDT compounds, alpha- and gamma-HCH, HCB, heptachlor epoxide, oxychlordane, cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor, and dieldrin in 9 marine mammal species: northern fur seal (Callorhinus ursinus), ringed seal (Phoca hispida), spotted seal (P. largha), bearded seal (Erignathus barbatus), pilot whale (Globicephala melas), harbor porpoise (Phocoena phocoena), white-sided dolphin (Lagenorhynchus acutus), beluga whale (Delphinapterus leucas), and bowhead whale (Balaena mysticetus). Analyses of beluga whale blubber for toxaphene and additional chlorinated hydrocarbons are obtained through collaboration with the Department of Fisheries and Oceans Canada.

Organochlorine contaminants in blubber of four seal species: integrating biomonitoring and specimen banking.

Blubber samples from four Alaska seal species (bearded seal, Erignathus barbatus, harbor seal, Phoca vitulina, northern fur seal, Callorhinus ursinus, ringed seal, P. hispida) were collected for inclusion in the US National Biomonitoring Specimen Bank, as well as for immediate analysis as part of the contaminant monitoring component of the US National Marine Fisheries Service's Marine Mammal Health and Stranding Response Program. The blubber samples were analyzed for organochlorine (OC) contaminants (e.g., PCB congeners, pesticides, DDTs). Results for bearded and ringed seals from the Alaska Arctic revealed low blubber concentrations of OC contaminants. Harbor seals from Prince William Sound. Gulf of Alaska, had somewhat higher blubber concentrations of OC contaminants. In contrast, northern fur seals sampled from the Pribilof Islands had blubber concentrations of certain OC contaminants that were about an order of magnitude higher than those found in the other seal species. Differences in contaminant concentrations among the Alaska seals may be explained by differences in feeding habits and migratory patterns, age or gender did not appear to account for the differences observed. The highest concentrations of OCs were found in harbor seals stranded along the northwestern US mainland, which is consistent with higher concentrations of anthropogenic contaminants being found in urban coastal areas than in more remote Arctic environments. The integration of real-time contaminant monitoring with specimen banking provides important baseline data that can be used to plan and manage banking activities. This includes identifying appropriate specimens that are useful in assessing temporal trends and increasing the utility of the banked samples in assessing chemical contaminant accumulation and relationships to biological effects.

Interlaboratory comparison study for PCB congeners and chlorinated pesticides in beluga whale blubber.

Three laboratories participated in an interlaboratory comparison exercise for the determination of polychlorinated biphenyl (PCB) congeners and chlorinated pesticides in Standard Reference Material (SRM) 1588 (Organics in Cod Liver Oil) a whale blubber control material, and six beluga whale (Delphinapterus leucas) blubber samples. The results are generally in good agreement. The minor disagreement of some of the results may be attributed to differences in detector calibrations, differences in chromatographic separation selectivity for specific compounds, or both. The SRM and control material help to validate the analytical procedures and to verify that these procedures remain in control.

Bioaccumulation of vanadium and other trace metals in livers of Alaskan cetaceans and pinnipeds.

Concentrations for 38 elements are routinely measured in the marine mammal liver tissues archived in the National Biomonitoring Specimen Bank (NBSB). Results show that hepatic concentrations of vanadium, selenium, silver, cadmium, and mercury are positively correlated with age for beluga whales (Delphinapterus leucas) and of vanadium, selenium, cadmium, and mercury with length for ringed seals (Phoca hispada). Many researchers have reported linear correlations of hepatic selenium, cadmium, and mercury with marine mammal age; however, there is only one other report of a linear correlation of hepatic vanadium with marine mammal age. Vanadium levels are at or below detection limits (< or = 0.01 micrograms/g) in liver tissues of U.S. east coast marine mammals from the NBSB but are present at levels ranging from 0.02 to 1.2 micrograms/g of wet weight in the tissues of Alaskan marine mammals. Although only three bearded seal (Eriganthus barbatus) and three bow-head whale (Balaena mysticetus) liver samples have been analyzed, hepatic vanadium levels also increased with animal size for these species. The presence of relatively high levels of vanadium in the livers of these Alaskan animals may reflect a unique dietary source of vanadium, a unique geochemical source of vanadium, or anthropogenic input to the Alaskan marine environment.

Trace element concentrations in cetacean liver tissues archived in the National Marine Mammal Tissue Bank.

The National Biomonitoring Specimen Bank (NBSB), a collaborative project of several U.S. government agencies, includes marine mammal tissues collected for the Alaska Marine Mammal Tissue Archival Project (AMMTAP) and the National Marine Mammal Tissue Bank (NMMTB). Tissues were collected from 139 animals representing 13 species of marine mammals from around the U.S. Recently, concentrations for up to 30 elements in liver tissues of nine long-finned pilot whales (Globicephala melas), six harbor porpoises (Phocoena phocoena), and four white-sided dolphins (Lagenorhynchus acutus) from the NMMTB were measured using instrumental neutron activation analysis. Results from analyses of these tissues are presented, compared with results for liver tissues from other marine mammals from the AMMTAP, and compared with published values.

Determination of PCBs and chlorinated hydrocarbons in marine mammal tissues.

Selected tissues (blubber, liver, kidney and muscle) from marine mammals, which were collected as part of the Alaska Marine Mammal Tissue Archival Project (AMMTAP), were analyzed for polychlorinated biphenyl (PCB) congeners and chlorinated pesticides. Concentrations of these compounds in the different tissues were compared and blubber was selected as the primary tissue for organic contaminant analyses for the AMMTAP based on higher levels (1-2 orders of magnitude) in this tissue compared to liver, kidney and muscle. Concentrations for 15 PCB congeners and 12 chlorinated pesticides are reported for 10 different animals of three species (northern fur seal, ringed seal and belukha whale) from five different sites.

Determination of inorganic constituents in marine mammal tissues.

Analyses of selected tissues from the Alaska Marine Mammal Tissue Archival Project (AMMTAP) have provided comprehensive information related to levels of 36 trace elements and methyl-mercury in marine mammal tissues. Liver, kidney and muscle tissues from two northern fur seals, four ringed seals and six belukha whales were analyzed. The bulk of the investigated tissues and additional tissues from a total of 65 marine mammals are banked in the AMMTAP. The results are compared to literature values for trace element concentrations in marine mammal tissues and their relevance to environmental studies is discussed.

Biological specimen banking in Arctic research: an Alaska perspective.

The cryogenic archival of biological specimens for retrospective analysis is of significant value for present and future research on population genetics, pathology, systematics, toxicology and environmental monitoring. This realization is emphasized by the increasing support of this activity by various government agencies, institutions and international groups. The international Arctic community is no exception. Canada has been conducting such activities in association with environmental monitoring programs for many years. Similar efforts appear to be underway in other polar nations. From the perspective of the United States Arctic, the Alaska Marine Mammal Tissue Archival Project (AMMTAP) was the earliest organized effort to develop an environmental specimen bank specifically designed for longterm archival of biological specimens under cryogenic conditions. The AMMTAP emphasizes use of standardized rigorous sampling and archival protocols, procedures that minimize contamination of samples during collection and maintaining a detailed record of sample history. The development of this specimen bank, recent activities of this project and other cryogenic specimen banks being developed in Alaska are described.

Alaskan marine mammal tissue archival project.

A project to establish an archive of Alaskan marine mammal tissues was conceived in 1987 to be a part of the National Biomonitoring Specimen Bank (NBSB). Protocols and field collection of marine mammals, long-term storage, and analysis are summarized in this paper. Instrumental neutron activation analysis has been used for an initial evaluation of trace element content in samples of northern fur seal (Callorhinus ursinus) from the Pribilof Islands. The findings agree with previously observed trace element levels in northern fur seals. The archived specimens can be used in future studies when comparison of past and present pollution levels are needed.