Mercury distribution in the skin of beluga (Delphinapterus leucas) and narwhal (Monodon monoceros) from the Canadian Arctic and mercury burdens and excretion by moulting.

Beluga and narwhal skin as a whole (in Inuktitut known as "muktuk") is considered to be a delicacy by native Canadian and Greenland people. Individual strata of the skin, and muscle from 27 beluga from the western, and 20 narwhal from the eastern Canadian Arctic, were analyzed for mercury and the thickness and density of each skin layer was measured. Mercury was not uniformly distributed in the skin, but increased outwardly with each layer. The concentration was only 0.29 and 0.16 microg/g (wet wt) in the innermost layer (dermis) of belugas and narwhal respectively, and 1.5 and 1.4 microg/g (wet wt) in the outermost layer (degenerative epidermis) of beluga and narwhal, respectively. There was a significant (alpha=0.05) association between age and mercury concentration in each skin layer, the regression coefficients progressively increasing from the inner layer (dermis) to the outer layer: 0.011-0.063 microg/g year-1; 0.034 microg/g year-1 for skin as a whole; 0.054 microg/g year-1 for muscle. The concentration of total mercury was 0.84 and 0.59 microg/g (wet wt) in skin as a whole (muktuk) of beluga and narwhal respectively, and 0.12 and 0.03 microg/g in blubber, respectively. The average, total mercury concentration in muscle tissue was 1.4 and 0.81 microg/g wet wt, in beluga and narwhal respectively, exceeding (except for blubber) the Canadian Government's Guideline (0.5 microg/g wet wt) for fish export and consumption. The skin surface area of an average-size beluga and narwhal was estimated (6.10 and 6.50 m2, respectively), as were excretions of mercury through moulting (13,861 and 6721 microg year-1; 14 and 7 mg year-1) for belugas and narwhal, respectively. The whole-body mercury burden (699,300 microg; 700 mg) for a 1000 kg beluga and its various tissues were estimated, as was the fraction of mercury excreted by moulting (2-0.42% of the whole-body burden). Annual mercury burden increments in beluga skin, muscle and the whole body were estimated (2750; 17,280; 40,00 microg year-1, respectively), using regression coefficients of age on mercury concentration. The annual gross mercury intake via food was estimated (131,400 microg), of which 70% was excreted.

Concentrations of mercury in tissues of beluga whales (Delphinapterus leucas) from several communities in the Canadian Arctic from 1981 to 2002.

Beluga whales have been hunted for food by Native People in the Canadian Arctic since prehistoric time. Here we report the results of analyses of total mercury in samples of liver, kidney, muscle and muktuk from collections over the period 1981-2002. We compare these results with human consumption guidelines and examine temporal and geographic variation. Liver has been analyzed more frequently than other organs and it has been used as the indicator organ. Mercury accumulates in the liver of the whales over time so that the whale ages are usually linked statistically to their levels of mercury in liver. Virtually all the samples of 566 animals analyzed contained mercury in liver at concentrations higher than the Canadian consumption guideline of 0.5 microg g-1 (wet weight) for fish. (There is no regulatory guideline for concentrations in marine mammals in Canada.) Samples from locations in the Mackenzie Delta in the western Canadian Arctic and from Pangnirtung in the eastern Canadian Arctic were obtained more often than from other location and these offered the best chances to determine whether levels have changed over time. Statistical outlier points were removed and the regressions of (ln) mercury in liver on age were used to calculate the level of mercury in whales of age 13.1 years in order to compare age-adjusted levels at different locations. These age-adjusted levels and also the slopes of regressions suggested that levels have increased in the Mackenzie Delta over the sampling period although not in a simple linear fashion. Other locations had fewer collections, generally spread over fewer years. Some of them indicated differences between sampling times but we could not establish whether these differences were simply temporal variation or whether they were segments of a consistent trend. For example, the levels in whales from Arviat were considerably higher in 1999 than in 1984 but we have only two samples. Similarly, samples from Iqaluit in 1994 exceeded considerably those in 1993 and the interval seems too short to reflect any regional temporal trend and more likely represent an extreme case of year-to-year variation. Previous analyses of data from geographically distinct groups had suggested that whales in the western Canadian Arctic had higher levels of mercury than those from the eastern Canadian Arctic. The present analysis suggests that such regional differences have diminished and are no longer statistically significant. No site has indicated significant decreases in more recent samples. The levels of total mercury in the most analyzed organs fell in the order of liver (highest levels), kidney, muscle and muktuk (lowest level). While muktuk had the lowest level of the organs most frequently analyzed, it is the preferred food item from these whales and it still exceeded the consumption guideline in most instances.

Mercury species in the liver of ringed seals.

Four types of mercury species, namely, methylmercury, organic mercury other than methylmercury, inorganic mercury, and insoluble mercury, deemed to be mercuric selenide (HgSe), were found in the liver of 45 ringed seals from the Canadian Arctic. On average, methylmercury, at 2%, made up the smallest fraction of the total mercury in the liver of these animals. Of the total mercury concentration in seal liver, 53% was insoluble mercury, estimated to be largely mercuric selenide. Other workers have found this compound to be present in mammalian liver and identified it to be HgSe. Organic mercury other than methylmercury made up 4%, and inorganic mercury 42% of the total mercury in the liver. The sum of the independently determined mercury species agreed well with the total mercury concentration in the liver. Species other than mercuric selenide are known to be toxic. Mercuric selenide, considered to be a stable end product of the demethylation process of methylmercury, although not readily eliminated from the liver, is inert and apparently non-toxic. Only approximately half of the total mercury in the liver was potentially toxic mercury. All four mercury species were positively correlated with the age of animals, the regression slope on age being 20 times larger for insoluble Hg (HgSe) than for methylmercury. A number of reported observations, such as the long half-life of Hg in liver (> or = 10 years), the dependence of Hg on age, and the often-observed one-to-one relationship between Hg and Se (on a molar basis), are readily explained by the temporal accumulation of HgSe in the liver. In the future, a more accurate assessment of the health risk to animals and humans from the consumption of contaminated animal tissues will be possible, by measuring all mercury species rather than just total mercury or methylmercury. Total mercury alone in the liver is an inadequate indicator of toxicity to animals. Methylmercury was analyzed by capillary gas-liquid chromatography with ECD detection, and the other species were operationally/experimentally defined using physical/chemical methods.

Spatial and temporal trends and effects of contaminants in the Canadian Arctic marine ecosystem: a review.

Recent studies have added substantially to our knowledge of spatial and temporal trends of persistent organic pollutants and heavy metals in the Canadian Arctic marine ecosystem. This paper reviews the current state of knowledge of contaminants in marine biota in the Canadian Arctic and where possible, discusses biological effects. The geographic coverage of information on contaminants such as persistent organochlorines (OCs) (PCBs, DDT- and chlordane-related compounds, hexachlorocyclohexanes, toxaphene) and heavy metals (mercury, selenium, cadmium, lead) in tissues of marine mammal and sea birds is relatively complete. All major beluga, ringed seal and polar bear stocks along with several major sea bird colonies have been sampled and analysed for OC and heavy metal contaminants. Studies on contaminants in walrus are limited to Foxe Basin and northern Québec stocks, while migratory harp seals have only been studied recently at one location. Contaminant measurements in bearded seal, harbour seal, bowhead whale and killer whale tissues from the Canadian Arctic are very limited or non-existent. Many of the temporal trend data for contaminants in Canadian Arctic biota are confounded by changes in analytical methodology, as well as by variability due to age/size, or to dietary and population shifts. Despite this, studies of OCs in ringed seal blubber at Holman Island and in sea birds at Prince Leopold Island in Lancaster Sound show declining concentrations of PCBs and DDT-related compounds from the 1970s to 1980s then a levelling off during the 1980s and early 1990s. For other OCs, such as chlordane, HCH and toxaphene, limited data for the 1980s to early 1990s suggests few significant declines in concentrations in marine mammals or sea birds. Temporal trend studies of heavy metals in ringed seals and beluga found higher mean concentrations of mercury in more recent (1993/1994) samples than in earlier collections (1981-1984 in eastern Arctic, 1972-1973 in western Arctic) for both species. Rates of accumulation of mercury are also higher in present day animals than 10-20 years ago. Cadmium concentrations in the same animals (eastern Arctic only) showed no change over a 10-year period. No temporal trend data are available for metals in sea birds or polar bears. There have been major advances in knowledge of specific biomarkers in Canadian Arctic biota over the past few years. The species with the most significant risk of exposure to PCBs and OC pesticides may be the polar bear which, based on comparison with EROD activity in other marine mammals (beluga, ringed seal), appears to have elevated CYP1A-mediated activity. The MFO enzyme data for polar bear, beluga and seals suggest that even the relatively low levels of contaminants present in Arctic animals may not be without biological effects, especially during years of poor feeding.

Methylmercury and total mercury in tissues of arctic marine mammals.

Concentrations of methylmercury, total mercury and selenium in marine mammal tissues were determined in liver, muscle, skin (muktuk) and blubber of belugas, ringed seals and narwhal, using atomic absorption and capillary gas chromatography with ECD detection. Mean MeHg levels in the types of tissues analysed, except blubber, generally exceeded the Canadian Federal Consumption Guideline for mercury in fish (0.5 micrograms/g wet wt.). A spatial trend of higher MeHg levels in western compared to eastern Arctic belugas and ringed seals was found which followed a similar trend observed for total mercury. Factors which could explain this trend are discussed. Robust linear regression of MeHg on total Hg and MeHg on age of animals was performed and a strong correlation between the two variables was found in each case. The ratio of MeHg to total mercury as indicated by the regression coefficients was close to one for muscle and skin (muktuk) while for liver it was < 1. The mean percentage of MeHg in the liver of marine mammals was 3-12% of the total Hg in this tissue depending on species and location. It is postulated that the formation and deposition of mercuric selenide in the liver is part of the demethylation process in this tissue. This is based on the relatively low fraction of MeHg in the liver not withstanding the fact that the predominant form of mercury taken up via food is MeHg. The long half-life for total mercury and the relatively short half-life for MeHg in this organ are in accord with this postulate as is the 1:1 stoichiometric relationship between mercury and selenium in the liver.

Overview and regional and temporal differences of heavy metals in Arctic whales and ringed seals in the Canadian Arctic.

Concentrations of mercury, cadmium, and other heavy metals in tissues of belugas (Delphinapterus leucas), narwhal (Monodon monoceros) and ringed seals (Phoca hispida) from across the Canadian Arctic are reported. Published and new information is used to provide an overview of metals in tissues of these animals, to delineate the existence of a spatial trend of mercury and cadmium in belugas and ringed seals, and to show a temporal trend is superimposed on the geochemical trend. Mercury concentrations in tissues of Arctic whales and ringed seals were high relative to the Canadian guideline of 0.5 micrograms/g wet wt., for mercury in fish, except in the skin of belugas (0.59-0.78 micrograms/g wet wt.) and flesh of ringed seals (0.39-0.41 micrograms/g wet wt.). In the flesh of belugas (0.94-1.34 micrograms/g wet wt.), and in the liver of ringed seals, tissues that are also consumed by Native people in the Arctic (8.34-27.5 micrograms/g wet wt.), the guideline value was significantly exceeded. Mean lead concentrations in tissues of belugas, narwhal and ringed seals were generally low (0.002-0.028 micrograms/g wet wt.), except in tissues of belugas in the St. Lawrence River (0.10-0.15 micrograms/g wet wt.). The concentration of zinc in the skin of whales was two to three times higher than in other tissues. The concentration of cadmium in organs was highest in narwhal. There was a positive correlation between mercury and selenium in the liver of all three species. The concentration of mercury in tissues of belugas and ringed seals was higher in the western than the eastern Arctic. This was attributed to different natural background concentrations in the western and eastern Arctic of Canada dictated by different geological formations in the two regions. Cadmium concentrations in tissues of belugas and ringed seals were higher in the eastern than the western Arctic. Zinc and copper in some tissues of belugas and ringed seals were also higher in the eastern than the western Arctic. Mercury in the liver of belugas was found to have increased in the western and eastern Arctic over 10-12 years. Mercury in the liver of ringed seals in the western Arctic and narwhal in the eastern Arctic showed similar increases. In recently collected belugas, the rate of accumulation of mercury in the liver was approximately twice that in belugas collected 10-12 years ago. In ringed seals, the rate was three times higher in recent samples compared to 15-20 years ago. There was no temporal change in cadmium levels in tissues of belugas, ringed seals or narwhal.

Presence and implications of chemical contaminants in the freshwaters of the Canadian Arctic.

Hydrocarbons, stable organochlorines, metals and radionuclides are widespread in the freshwaters of the Canadian Arctic. Petroleum-associated hydrocarbon sources include natural seepage, wastes and effluents from exploration, production and refining at Norman Wells and spills. Hydrocarbons also originate from combustion of carbon-based fuels, generally at lower latitudes and then reach the Arctic with air movements. Organochlorine compounds also move throughout the hemisphere by aerial pathways and have become distributed widely in Arctic fish. The organochlorine at highest concentration in Arctic freshwater is alpha-HCH, while those generally at highest concentrations in the fish are toxaphene, PCBs and chlordane. Metals are ubiquitous in Arctic freshwaters, with inputs of several metals by precipitation superimposed on natural geologic backgrounds. Mercury is found in muscle of fish from Arctic freshwaters at concentrations up to about 0.5 ppm. Radionuclides are also widespread at levels below those acceptable in food, with some local elevations near former mines. The implications of these contaminants for the northern ecosystems and the people dependent upon them are still not clear. Preliminary studies of inducible enzymes in fish suggest that the thresholds for biological damage have not been reached.

Arctic marine ecosystem contamination.

The current state of knowledge of levels, spatial and temporal trends of contaminants in the Arctic marine ecosystem varies greatly among pollutants and among environmental compartments. Levels of polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and some heavy metals such as mercury and lead, in Arctic marine mammals and fish are relatively well documented because of the need for comparisons with biota in more polluted environments and interest in the contamination of native diets. Levels of heavy metals, alkanes, polyaromatic hydrocarbons (PAH) and OCs in the Arctic Ocean are comparable to uncontaminated ocean waters in the mid-latitudes. But concentrations of alpha- and gamma-hexachlorocyclohexane (HCHs) are higher in northern waters far removed from local sources, possibly because lower water temperature reduces transfer to the atmosphere. Bioaccumulation of OCs and heavy metals in Arctic marine food chains begins with epontic ice algae or phytoplankton in surface waters. Polychlorinated camphenes (PCC), PCBs, DDT- and chlordane-related compounds are the major OCs in marine fish, mammals and seabirds. Mean concentrations of most PCBs and OC pesticides in ringed seal (Phoca hispida) and polar bear (Ursus maritimus) populations in the Canadian Arctic are quite similar indicating a uniform geographic distribution of contamination, although alpha-HCH showed a distinct latitudinal gradient in bears due to higher levels in zones influenced by continental runoff. Ringed seals from Spitzbergen have higher levels of PCBs, total DDT and polychlorinated dioxins/furans (PCDD/PCDFs). In contrast to other OCs, PCDD/PCDFs in Canadian Arctic ringed seals and polar bears were higher in the east/central Arctic than at more southerly locations. Remarkably high cadmium levels are found in kidney and liver of narwhal (Monodons monoceros) from western Baffin Bay (mean of 63.5 micrograms g-1) and western Greenland waters (median of 39.5 micrograms g-1). Mercury concentrations in muscle of ringed seal and cetaceans frequently exceed 0.5 microgram g-1 especially in older animals. Cadmium concentrations in polar bear liver increased from west to east, while mercury levels were higher in ringed seals from the western Canadian Arctic, which suggests that natural sources of these metals predominate. Studies of temporal trends in OCs in ringed seals and seabirds in the Canadian Arctic indicate PCB and DDT levels declined significantly from the early 1970s to the 1980s. There is a lack of temporal trend data for other OC pesticides as well as for heavy metals and hydrocarbons.(ABSTRACT TRUNCATED AT 400 WORDS)

Trace metal determination in animal tissues: an interlaboratory comparison.

Two dried and powdered preparations of narwhal liver and muscle were distributed to 13 laboratories for analysis for Cu, Cd, Zn, Pb, Hg, and Se. Laboratories chose their own methods, using atomic-absorption spectrometry, atomic-emission spectrometry with a direct-current or inductively-coupled plasma, anodic stripping voltammetry (ASV), neutron activation analysis (NAA), and gas chromatography. The coefficients of variation ranged from 2 to 5% for Cu, Cd, Zn, Hg in liver, but were somewhat higher for Zn by ASV and NAA. In muscle, the precision for Zn was similar to that for liver, but was poorer for Cu (8.8%) and Cd (19%). For Pb, the overall precision was 15% and 21% for liver and muscle respectively. Selenium in both tissues was determined with an overall precision of 6-7%, except by NAA, for which it was considerably worse, at 21-26%.

Low-molecular weight metalloproteins in tissues of the narwhal (Monodon monoceros).

Narwhal (Monodon monoceros) liver and kidney cytosol were fractionated by gel chromatography, anion-exchange chromatography and electrophoresis. Cadmium was associated largely with low molecular weight proteins, while mercury was associated also with high molecular weight proteins, but apparently not because of saturation of the metallothionein mechanism. Eight different electrophoretic bands, four of which were metalloproteins, were found under the "metallothionein" peak. Anion-exchange chromatography yielded five metal peaks while further fractionation on G-50 gave two peaks, one containing almost pure metallothionein (Mt-1) and the other a metalloprotein having twice the molecular weight of metallothionein. Mt-2 was observed, at a much lower concentration than Mt-1, in liver but not kidney.

Subcellular distribution of heavy metals in liver and kidney of a narwhal whale (Monodon monoceros): an evaluation for the presence of metallothionein.

The subcellular distribution of Zn, Cd, Cu and Hg in liver and kidney from a narwhal was determined by ultracentrifugation and gel filtration. Most of the total mercury in the liver and kidney was bound by the cellular pellet (88 and 73%, respectively). Of the total mercury, 7 and 11% was in the form of methylmercury in the liver and kidney, respectively. More than half (74%) of the total Zn and Cu in the kidney was in the cytosol and somewhat less than this was in the cytosol of the liver. Almost all of the cadmium in liver and kidney (88 and 92%, respectively) was in cytosol. Cytosolic fractions from liver and kidney were evaluated for the presence of metallothionein by analysing for Zn, Cd, Hg, Cu, Fe and--SH groups, by molecular weight estimation and by u.v. absorption spectra. Metallothionein was found in these organs in estimated concentrations similar to those present in terrestrial and other marine mammals.

Arsenic in sediments, water and aquatic biota from lakes in the vicinity of Yellowknife, Northwest Territories, Canada.

Arsenic concentrations were measured in aquatic invertebrates, macrophytes, sediments, and water of lakes in the vicinity of Yellowknife (N.W.T.), Canada. In arsenic-contaminated lakes the arsenic concentration ranged from 0.70 to 5.5 ppm in water, 6 to 3,500 ppm in bottom sediments, 150 to 3,700 ppm in macrophytes, 700 to 2,400 ppm in zooplankton, and less than 1 to 1,300 ppm in other invertebrates. The arsenic concentration in invertebrates varied with sampling time, place, and taxon. Arsenic concentration factors were calculated, and found to decrease with increasing concentration of arsenic in ecosystem components of the lake. No evidence was found for biomagnification of arsenic through ascending trophic levels. In high-arsenic lakes herbivores had the highest arsenic concentrations, and omnivores the lowest. Pelecypoda, Ephemeroptera, Amphipoda, and Hirudinea were conspicuously absent from high-arsenic lakes. These particular organisms may be more susceptible to the effects of arsenic than others.

Chronic toxicity of a synthetic tri-aryl phosphate oil to fish.

Rainbow trout (Salmo gairdneri) were exposed to IMOL S-140, a synthetic high-temperature lubricating oil composed of tri-aryl phosphates and, although no sign of acute toxicity was evident, the fish slowly developed symptoms of chronic posioning. Thus, floating food pellets were refused, the activities of glutamic oxalacetic transaminase and lactate dehydrogenase in serum were greatly elevated, and internal fatty tissues became discoloured. Neither serum nor brain cholinesterase activities were inhibited.