Elizabeth A. Mackey

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 (⩽0.01 μg/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 μg/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.

Relationship of silver with selenium and mercury in the liver of two species of toothed whales (odontocetes)

Liver specimens archived in the National Biomonitoring Specimen Bank from beluga whales, Delphinapterus leucas, and from Alaska and pilot whales, Globicephala melas, from the North Atlantic were analysed for silver, selenium and total mercury. Silver concentrations in beluga whales were one to three orders of magnitude higher than the concentrations in pilot whales and those reported elsewhere for other marine mammals. The concentrations of silver in the livers of beluga whales were the same or in some instances higher than the concentrations of selenium or mercury. Like mercury, silver was positively correlated with selenium in both pilot and beluga whales. This suggests a possible role for selenium in the accumulation and storage of silver in both species of whales, and raises questions about the potential for silver at such high concentrations to affect radical-scavenging enzyme systems in these marine mammals.

Determination of arsenic compounds in marine mammals with high-performance liquid chromatography and an inductively coupled plasma mass spectrometer as element-specific detector

Total arsenic concentrations and the concentrations of individual arsenic compounds were determined in liver samples of pinnipeds [nine ringed seals (Phoca hispida), one bearded seal (Erginathus barbatus)] and cetaceans [two pilot whales (Globicephalus melas), one beluga whale (Deliphinapterus leucus)]. Total arsenic concentrations ranged from 0.167 to 2.40 mg As kg -1 wet mass. The arsenic compounds extracted from the liver samples with a methanol/water mixture (9:1, v/v) were identified and quantified by anion- and cation-exchange chromatography. An ICP-MS equipped with a hydraulic highpressure nebulizer served as the arsenic-specific detector. Arsenobetaine (0.052-1.67 mg As kg -1 wet mass) was the predominant arsenic compound in all the liver samples. Arsenocholine was present in all livers (0.005-0.044 mg As kg -1 wet mass). The tetramethylarsonium cation was detected in all pinnipeds (<0.009 to 0.043 mg Askg -1 ) but not in any of the cetaceans. The concentration of dimethylarsinic acid ranged from < 0.001 to 0.109mgAskg -1 wet mass. Most of the concentrations for methylarsonic acid (<0.001 to 0.025 mg As kg -1 wet mass) were below the detection limit. Arsenous acid and arsenic acid concentrations were below the detection limit of the method (0.001 mg As kg -1 ). An unknown arsenic compound was present in all liver samples at concentrations from 0.002-0.027 mg As kg -1 .

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.

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.

Development of frozen whale blubber and liver reference materials for the measurement of organic and inorganic contaminants

SummaryFresh frozen homogenates of pilot whale blubber and liver tissue were prepared for use as control materials for the determination of organic and inorganic contaminants in marine mammal tissue analyses. The blubber material was analyzed to determine 30 polychlorinated biphenyl congeners and 16 chlorinated pesticides using gas chromatography with electron capture detection and gas chromatographymass spectrometry. A total of 39 trace elements and methylmercury were determined in the liver homogenate using instrumental neutron activation analysis, voltammetry, and cold vapor atomic absorption spectroscopy. The preparation and analysis of these two tissue materials are part of the development of marine mammal tissue reference materials.

Neutron captue prompt gamma-ray activation analysis at the NIST Cold Neutron Research Facility

An instrument for neutron capture prompt gamma-ray activation analysis (PGAA) has been constructed as part of the Cold Neutron Research Facility at the 20 MW National Institute of Standards and Technology Research Reactor. The neutron fluence rate (thermal equivalent) is 1.5·108 n ·cm−2·s−1, with negligible fast neutrons and gamma-rays. With compact geometry and hydrogen-free construction, the sensitivity is sevenfold better than an existing thermal instrument. Hydrogen background is thirtyfold lower.

Neutron scattering by hydrogen in cold neutron prompt gamma-activation analysis

The effects of neutron scattering by hydrogen within targets for cold neutron prompt γ-ray activation analysis (CNPGAA) have been characterized. For most targets studied, the probability for neutron absorption, and hence CNPGAA sensitivities (counts·s−1·mg−1), decrease with increasing H content and with target thickness. Comparisons with results from thermal neutron PGAA indicate that the effects of cold neutron scattering differ from those of thermal neutron scattering. CNPGAA sensitivities for “l/v” nuclides show similar sensitivity decreases, while Sm sensitivities show smaller decreases.

Scattering and absorption effects in neutron beam activation analysis experiments

We have investigated the effects of scattering and absorption in neutron beam activation analysis experiments, both by direct measurement and by Monte Carlo simulation. Significant sensitivity enhancements occur for thin disks placed at 45° to the beam but very much smaller effects occur for spheres. The agreement between measurement and calculation is generally good.

Use of INAA, PGAA, and RNAA to determine 30 elements for certification of an SRM: Tomato Leaves, 157a

Analyses for certification have been made for the determination of 30 elements in the National Institute of Standards and Technology (NIST) Tomato Leaves renewal reference material, SRM 1573a. Three of the analytical techniques used were instrumental neutron activation analysis (INAA), radiochemical neutron activation analysis (RNAA), and prompt gamma activation analysis (PGAA). These techniques provided data on 19 elements by INAA, 10 elements by PGAA, and 7 elements by RNAA, with some overlap between techniques. For example, INAA was able to obtain overall analytical uncerainties (at the 95% confidence level) averaging ±2.2% for major and minor constituents (Ca, Mg, K), ±3.3% for constituents from 1 to 1000 μg/g (Na, Fe, Al, Mn, Ba, Zn, Rb, La, Cr), and ±6.4% for elements between 10 and 1000 ng/g (Co, V, Se, Th, Sc, Sb), using sample dry weights of approximately 150 mg. These analyses represent the most extensive use to date of nuclear analytical techniques in the certification of a trace element SRM at NIST.