Updated Global and Oceanic Mercury Budgets for the United Nations Global Mercury Assessment 2018.

In support of international efforts to reduce mercury (Hg) exposure in humans and wildlife, this paper reviews the literature concerning global Hg emissions, cycling and fate, and presents revised global and oceanic Hg budgets for the 2018 United Nations Global Mercury Assessment. We assessed two competing scenarios about the impacts of 16th - late 19th century New World silver (Ag) mining, which may be the largest human source of atmospheric Hg in history. Consideration of Ag ore geochemistry, historical documents on Hg use, and comparison of the scenarios against atmospheric Hg patterns in environmental archives, strongly support a "low mining emission" scenario. Building upon this scenario and other published work, the revised global budget estimates human activities including recycled legacy emissions have increased current atmospheric Hg concentrations by about 450% above natural levels (prevailing before 1450 AD). Current anthropogenic emissions to air are 2.5 ± 0.5 kt/y. The increase in atmospheric Hg concentrations has driven a ∼ 300% average increase in deposition, and a 230% increase in surface marine waters. Deeper marine waters show increases of only 12-25%. The overall increase in Hg in surface organic soils (∼15%) is small due to the large mass of natural Hg already present from rock weathering, but this figure varies regionally. Specific research recommendations are made to reduce uncertainties, particularly through improved understanding of fundamental processes of the Hg cycle, and continued improvements in emissions inventories from large natural and anthropogenic sources.

Isotopic evolution of atmospheric Pb from metallurgical processing in Flin Flon, Manitoba: Retrospective analysis using peat cores from bogs.

Atmospheric Pb deposition was reconstructed using peat cores from bogs in the vicinity of Flin Flon, Manitoba, Canada, home to a zinc refinery and copper smelter. The Sask Lake (SL4-1) core was collected 85 km NW of Flin Flon and Kotyk Lake (KOL) 30 km NE. The distribution of Sr and U show that both profiles are predominantly minerotrophic (ie groundwater-fed), but the Pb concentration profile shows that Pb was received exclusively from the atmosphere. Graphs of 208Pb/206Pb against 206Pb/207Pb document atmospheric Pb contamination dating from the early to mid-1800's, well before the start of metallurgical processing (in 1930) and attributable to long-range atmospheric transport from other regions of North America. Industrial activities at Flin Flon clearly affected the concentrations, enrichment factor (calculated using Sc), and accumulation rates of Pb, but it is the similarity in isotopic composition, and contrast with crustal values (206Pb/207Pb ca. 1.20 to 1.22) which makes the connection to the Flin Flon ores. The KOL samples dating from 1925-1976 CE have a 206Pb/207Pb of 1.032 ± 0.002 (n = 11) which approach the values for the Flin Flon ores (206Pb/207Pb = 1.008). But even at SL4-1, the peat samples dating from 1925-1976 CE have a 206Pb/207Pb of 1.061 ± 0.022 (n = 18) which is well below the corresponding ratio of Canadian leaded gasoline (206Pb/207Pb = ca. 1.15). The SL4-1 site too, therefore, was clearly impacted by Pb from mining and metallurgy, despite the distance (88 km) from Flin Flon and being predominantly upwind. These two bogs not only provide the chronology of atmospheric Pb deposition for the past decades, but suggest that the extent of contamination may have been underestimated by previous studies.

A test of the stability of Cd, Cu, Hg, Pb and Zn profiles over two decades in lake sediments near the Flin Flon Smelter, Manitoba, Canada.

Lake sediments are valuable archives of atmospheric metal deposition, but the stability of some element profiles may possibly be affected by diagenetic changes over time. In this extensive case study, the stability of sedimentary Cd, Cu, Hg, Pb and Zn profiles was assessed in dated sediment cores that were collected in 2004 from four smelter-affected lakes near Flin Flon, Manitoba, which had previously been cored in 1985. Metal profiles determined in 1985 were in most cases clearly reproduced in the corresponding sediment layers in 2004, although small-scale spatial heterogeneity in metal distribution complicated the temporal comparisons. Pre-smelter (i.e. pre-1930) increases in metal profiles were likely the result of long-range atmospheric metal pollution, coupled with particle mixing at the 1930s sediment surface. However, the close agreement between key inflection points in the metal profiles sampled two decades apart suggests that metals in most of the lakes, and Hg and Zn in the most contaminated lake (Meridian), were stable once the sediments were buried below the surface mixed layer. Cadmium, Cu and Pb profiles in Meridian Lake did not agree as well between studies, showing evidence of upward remobilization over time. Profiles of redox-indicator elements (Fe, Mn, Mo and U) suggested that the rate of Mn oxyhydroxide recycling within sediment was more rapid in Meridian Lake, which may have caused the Cd, Cu and Pb redistribution.

How well do environmental archives of atmospheric mercury deposition in the Arctic reproduce rates and trends depicted by atmospheric models and measurements?

This review compares the reconstruction of atmospheric Hg deposition rates and historical trends over recent decades in the Arctic, inferred from Hg profiles in natural archives such as lake and marine sediments, peat bogs and glacial firn (permanent snowpack), against those predicted by three state-of-the-art atmospheric models based on global Hg emission inventories from 1990 onwards. Model veracity was first tested against atmospheric Hg measurements. Most of the natural archive and atmospheric data came from the Canadian-Greenland sectors of the Arctic, whereas spatial coverage was poor in other regions. In general, for the Canadian-Greenland Arctic, models provided good agreement with atmospheric gaseous elemental Hg (GEM) concentrations and trends measured instrumentally. However, there are few instrumented deposition data with which to test the model estimates of Hg deposition, and these data suggest models over-estimated deposition fluxes under Arctic conditions. Reconstructed GEM data from glacial firn on Greenland Summit showed the best agreement with the known decline in global Hg emissions after about 1980, and were corroborated by archived aerosol filter data from Resolute, Nunavut. The relatively stable or slowly declining firn and model GEM trends after 1990 were also corroborated by real-time instrument measurements at Alert, Nunavut, after 1995. However, Hg fluxes and trends in northern Canadian lake sediments and a southern Greenland peat bog did not exhibit good agreement with model predictions of atmospheric deposition since 1990, the Greenland firn GEM record, direct GEM measurements, or trends in global emissions since 1980. Various explanations are proposed to account for these discrepancies between atmosphere and archives, including problems with the accuracy of archive chronologies, climate-driven changes in Hg transfer rates from air to catchments, waters and subsequently into sediments, and post-depositional diagenesis in peat bogs. However, no general consensus in the scientific community has been achieved.

Comparison of mercury and zinc profiles in peat and lake sediment archives with historical changes in emissions from the Flin Flon metal smelter, Manitoba, Canada.

The copper-zinc smelter at Flin Flon, Manitoba, was historically the largest single Hg point-source in Canada, as well as a major source of Zn. Although emissions were reported by industry to have declined significantly since the late 1980s, these reductions have never been independently verified. Here, the histories of Hg and Zn deposition over the past century or more were determined at five lake sediment and three peat study sites in the surrounding region. At sites spanning the range from heavy to minor pollution, lake sediment Hg and Zn concentration and flux profiles increased significantly in the early 1930s after the smelter opened. Two of the three peat archives were wholly or partially compromised by either physical disturbances or biogeochemical transitions which reduced their effectiveness as atmospheric metal deposition recorders. But the remaining peat records, including a detailed recent 20 yr record at a moderately polluted site, appeared to show that substantive reductions in metal levels had occurred after the late 1980s, coincident with the reported emission reductions. However, the lake sediment results, taken at face value, contradicted the peat results in that no major declines in metal concentrations or fluxes occurred over recent decades. Mercury and Zn fluxes have in fact increased substantially since 1988 in most lakes. We suggest that this discrepancy may be explained by catchment soil saturation by historically deposited metals which are now mobilizing and leaching into lakes, as has been reported from other smelter polluted systems in Canada, whereas the upper sections of the peat cores reflected recent declines in atmospheric deposition. However, further research including instrumented wet and dry deposition measurements and catchment/lake mass balance studies is recommended to test this hypothesis, and to provide definitive data on current atmospheric metal deposition rates in the area.

Increasing contaminant burdens in an arctic fish, Burbot ( Lota lota ), in a warming climate.

The temporal patterns of mercury (Hg), polychlorinated biphenyls (PCBs), and other contaminants in Arctic aquatic biota are usually attributed to changing atmospheric sources. However, climate variability and change is another means of altering contaminant fate and bioavailability. We show here that the concentrations of Hg and PCBs in Mackenzie River burbot ( Lota lota ), a top predator fish and important staple food for northern Canadian communities, have increased significantly over the last 25 years despite falling or stable atmospheric concentrations, suggesting that environmental processes subsequent to atmospheric transport are responsible. Using a dated sediment core from a tributary lake near the Mackenzie River sampling site, we show that variations in Hg concentrations downcore are strongly associated with labile, algal-derived organic matter (OM). Strong temporal correlations between increasing primary productivity and biotic Hg and PCBs as reflected by burbot suggest that warming temperatures and reduced ice cover may lead to increased exposure to these contaminants in high trophic level Arctic freshwater biota.

Historical interrelated variations of mercury and aquatic organic matter in lake sediment cores from a subArctic lake in Yukon, Canada: further evidence toward the algal-mercury scavenging hypothesis.

This study investigates the role of climate-driven aquatic productivity increases in conrolling the sedimentary accumulation of mercury (Hg) in Kusawa Lake, Yukon, Canada. Organic geochemistry data reveals a significant link between the increasing trends of Hg and of labile algal-derived organic matter (OM) over the centuries and in particular over recent decades. Sedimentary Hg accumulation rates continue to increase even though atmospheric concentrations of Hg have remained the same or even declined. Together, these findings indicate that the significant rise in Hg content recorded in the sediments since the early 1950s may not be representative of increasing atmospheric Hg levels but are strongly influenced by elevated concentrations of algal-derived OM in the water-column. These likely increase the scavenging rate of "available" Hg from the water column. Therefore, recent increases in algal productivity may result in overestimation of the historical rates of atmospheric Hg deposition recorded in the sediments. This study confirms earlier published findings from two High Arctic lakes, and shows that the Hg-OM scavenging hypothesis may also apply to sub-Arctic lakes.

Long-term changes of mercury levels in ringed seal (Phoca hispida) from Amundsen Gulf, and beluga (Delphinapterus leucas) from the Beaufort Sea, western Canadian Arctic.

Mercury (Hg) concentrations were determined in the canine teeth of ringed seals (Phoca hispida) harvested during the 13th-14th, late 19th and early 21st Centuries in Amundsen Gulf, Northwest Territories, Canada. Most historical and pre-industrial teeth contained undetectable Hg levels (i.e. <1.0 ng/g DW), whereas samples from 2001-03 contained up to 12 ng/g DW in an age-dependent pattern. Assuming a median [Hg] value in 13th-14th Century teeth of half the detection limit (i.e. 0.5 ng/g DW), geometric means of Hg in modern teeth were 9-17 times those of seals in the 14th Century, equivalent to an anthropogenic input of 89-94% of total Hg in modern seals. These results corroborate a previous study of beluga (Delphinapterus leucas) in the nearby Beaufort Sea. While the seals' trophic position (inferred from delta(15)N values) did not change over time, modern delta(13)C values were lower by about 2 per thousand than in the 14th and 19th Centuries. This could be due to increased dissolution of anthropogenically derived CO(2) in the ocean from the atmosphere, but could also indicate more offshore pelagic feeding by modern seals, which might be a factor in their Hg exposure. New tooth [Hg] data are also presented for the Beaufort Sea beluga, using recently-discovered museum samples collected in 1960/61, which showed that most of the anthropogenic contribution to beluga Hg had already taken effect by 1960 (reaching approximately 75% of total Hg). Taken together, the long-term seal and beluga data indicate that whereas Hg levels in the marine ecosystems of the western Canadian Arctic were probably unchanged from pre-industrial times up to the late 19th Century, there was a significant, many-fold increase in the early to mid-20th Century, but little or no change after about the early 1960s.

Mercury, lead and lead isotope ratios in the teeth of moose (Alces alces) from Isle Royale, U.S. Upper Midwest, from 1952 to 2002.

Assessing the effect of recent reductions in atmospheric pollution on metal concentrations in wildlife in North America has been difficult because of the sparse availability of historical samples with which to establish a "pre-regulation" baseline, and because many ecosystems may be affected by local point sources which could obscure broader-scale trends. Here we report a recent 50 yr annual record of Hg, Pb and Pb isotope ratios in the teeth of a resident population of moose (Alces alces) in Isle Royale National Park, a relatively remote island in Lake Superior, Michigan, USA. During the early 1980s, concentrations of tooth Hg abruptly declined by approximately 65% compared to the previous 30 years (p<0.001), similar to a previous study of Hg in herring gull eggs in the Great Lakes region. Lead declined at the same time, and by 2002 Pb in adult moose teeth was approximately 80% lower than it had been prior to the early 1980s (p<0.001). These trends were unaffected by normalization against the geogenic elements La and Sr, which indicates that the trends in Hg and Pb had an anthropogenic cause. Temporal patterns of Pb isotope ratios suggested that the primary sources of Pb at different times in the moose were combustion of U.S. coal and leaded gasoline. Reductions in emissions from coal combustion might explain the co-incident reductions of Hg and Pb in Isle Royale moose, with elimination of alkyl Pb additives also playing a role in the continued tooth Pb reductions after 1983.

Evidence for control of mercury accumulation rates in Canadian High Arctic lake sediments by variations of aquatic primary productivity.

Climate warming in the 20th Century has had profound effects on the limnology of High Arctic lakes, including substantial increases in autochthonous primary productivity (APP). Here, we report organic carbon and Hg core profiles from two lakes which support the hypothesis that 20th Century increases in sedimentary Hg at these latitudes were largely driven by APP increases, via Hg scavenging by algae and/or suspended detrital algal matter. Hydrocarbons quantitatively released by thermal cracking of algal-derived organic matter ("S2" carbon) were used to reconstruct past APP. Variation of S2 flux accounted for 87-91% of the variance in total Hg flux in the study lakes since 1854. Mercury and S2 carbon were also associated during the pre-Industrial Period, co-varying by as much as 30% during past warm/cool periods. As a test of the hypothesis, predicted values for 20th Century [Hg] were derived from pre-1900 Hg-S2 relationships. Measured 20th Century [Hg] was on average only 6-11% higher than that predicted in one lake, and 33% higher in the other. S2-normalization of [Hg] in the latter lake suggested that 78% of the average increase in 20th Century [Hg] could be explained by scavenging. These findings suggest that the atmospheric contribution of long-range anthropogenic Hg to High Arctic lakes may have been overestimated by several-fold because of this climate-driven process, and was responsible for no more than 22% of the 20th Century [Hg] increase in the study lakes.

Changes in mercury and cadmium concentrations and the feeding behaviour of beluga (Delphinapterus leucas) near Somerset Island, Canada, during the 20th century.

Beluga (Delphinapterus leucas) continues to be an important food species for Arctic communities, despite concerns about its high mercury (Hg) content. We investigated whether Hg and cadmium (Cd) concentrations had changed during the 20th century in beluga near Somerset Island in the central Canadian Arctic, using well-preserved teeth collected from historical sites (dating to the late 19th century and 1926-1947) and during subsistence hunts in the late 1990s. Mercury concentrations in both historical and modern teeth were correlated with animal age, but 1990s beluga exhibited a significantly more rapid accumulation with age than late 19th century animals, indicating that Hg concentrations or bioavailability in their food chain had increased during the last century. The geometric mean tooth Hg concentration in modern 30 year old animals was 7.7 times higher than in the late 19th century, which corresponds to threefold higher concentrations in muktuk and muscle. Teeth from 1926 to 1947 were similar in Hg content to the late 19th century, suggesting that the increase had occurred sometime after the 1940s. In contrast, tooth Cd was not correlated with animal age and decreased during the last 100 years, indicating that anthropogenic Cd was negligible in this population. Late 19th century beluga displayed a greater range of prey selection (tooth delta15N values: 15.6-20.5 per thousand) than modern animals (delta15N: 17.2-21.1 per thousand). To prevent this difference from confounding the temporal Hg comparison, the Hg-age relationships discussed above were based on historical animals, which overlapped isotopically with the modern group. Tooth delta13C also changed to isotopically more depleted values in modern animals, with the most likely explanation being a significant shift to more pelagic-based feeding. Industrial Hg pollution is a plausible explanation for the recent Hg increase. However, without further investigation of the relationship between the range exploitation of modern beluga and their possible exposure to regional marine food chains with (naturally) higher Hg contents than their historical counterparts, we cannot unequivocally conclude that the increase was anthropogenically driven.

Persistent organic pollutants and mercury in marine biota of the Canadian Arctic: an overview of spatial and temporal trends.

This review summarizes and synthesizes the significant amount of data which was generated on mercury (Hg) and persistent organic pollutants (POPs) in Canadian Arctic marine biota since the first Canadian Arctic Contaminants Assessment Report (CACAR) was published in 1997. This recent body of work has led to a better understanding of the current levels and spatial and temporal trends of contaminants in biota, including the marine food species that northern peoples traditionally consume. Compared to other circumpolar countries, concentrations of many organochlorines (OCs) in Canadian Arctic marine biota are generally lower than in the European Arctic and eastern Greenland but are higher than in Alaska, whereas Hg concentrations are substantially higher in Canada than elsewhere. Spatial coverage of OCs in ringed seals, beluga and seabirds remains a strength of the Arctic contaminant data set for Canada. Concentrations of OCs in marine mammals and seabirds remain fairly consistent across the Canadian Arctic although subtle differences from west to east and south to north are found in the proportions of various chemicals. The most significant development since 1997 is improvement in the temporal trend data sets, thanks to the use of archived tissue samples from the 1970s and 1980s, long-term studies using archeological material, as well as the continuation of sampling. These data cover a range of species and chemicals and also include retrospective studies on new chemicals such as polybrominated diphenyl ethers. There is solid evidence in a few species (beluga, polar bear, blue mussels) that Hg at some locations has significantly increased from pre-industrial times to the present; however, the temporal trends of Hg over the past 20-30 years are inconsistent. Some animal populations exhibited significant increases in Hg whereas others did not. Therefore, it is currently not possible to determine if anthropogenic Hg is generally increasing in Canadian Arctic biota. It is also not yet possible to evaluate whether the recent Hg increases observed in some biota may be due solely to increased anthropogenic inputs or are in part the product of environmental change, e.g., climate warming. Concentrations of most "legacy" OCs (PCBs, DDT, etc.) significantly declined in Canadian Arctic biota from the 1970s to the late 1990s, and today are generally less than half the levels of the 1970s, particularly in seabirds and ringed seals. Chlorobenzenes and endosulfan were among the few OCs to show increases during this period while summation operatorHCH remained relatively constant in most species. A suite of new-use chemicals previously unreported in Arctic biota (e.g., polybrominated diphenyl ethers (PBDEs), short chain chlorinated paraffins (SCCPs), polychlorinated naphthalenes (PCNs), perfluoro-octane sulfonic acid (PFOS) and perfluorocarboxylic acids (PFCAs)) has recently been found, but there is insufficient information to assess species differences, spatial patterns or food web dynamics for these compounds. Concentrations of these new chemicals are generally lower than legacy OCs, but there is concern because some are rapidly increasing in concentration (e.g., PBDEs), while others such as PFOS have unique toxicological properties, and some were not expected to be found in the Arctic because of their supposedly low potential for long-range transport. Continuing temporal monitoring of POPs and Hg in a variety of marine biota must be a priority.

Modern and historical fluxes of halogenated organic contaminants to a lake in the Canadian arctic, as determined from annually laminated sediment cores.

Two annually laminated cores collected from Lake DV09 on Devon Island in May 1999 were dated using 210Pb and 137Cs, and analyzed for a variety of halogenated organic contaminants (HOCs), including polychlorinated biphenyls (PCBs), organochlorine pesticides, short-chain polychlorinated n-alkanes (sPCAs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polybrominated diphenyl ethers (PBDEs). Dry weight HOC concentrations in Lake DV09 sediments were generally similar to other remote Arctic lakes. Maximum HOC fluxes often agreed well with production maxima, although many compound groups exhibited maxima at or near the sediment surface, much later than peak production. The lower than expected HOC concentrations in older sediment slices may be due to anaerobic degradation and possibly to dilution resulting from a temporary increase in sedimentation rate observed between the mid-1960s and 1970s. Indeed, temporal trends were more readily apparent for those compound classes when anaerobic metabolites were also analyzed, such as for DDT and toxaphene. However, it is postulated here for the first time that the maximum or increasing HOC surface fluxes observed for many of the major compound classes in DV09 sediments may be influenced by climate variation and the resulting increase in algal primary productivity which could drive an increasing rate of HOC scavenging from the water column. Both the fraction (F(TC)) and enantiomer fraction (EF) of trans-chlordane (TC) decreased significantly between 1957 and 1997, suggesting that recent inputs to the lake are from weathered chlordane sources. PCDD/Fs showed a change in sources from pentachlorophenol (PeCP) in the 1950s and 1960s to combustion sources into the 1990s. Improvements in combustion technology may be responsible for the reducing the proportion of TCDF relative to OCDD in the most recent slice.

Baleen as a biomonitor of mercury content and dietary history of North Atlantic minke whales (Balaenopetra acutorostrata): combining elemental and stable isotope approaches.

Baleen is an incrementally-growing tissue of balaenopteran whales which preserves relatively well over time in museums and some archeological sites, and, therefore might be useful for studies examining long-term changes of metal levels in whales. This study examined Hg and stable C and N isotopic composition of baleen plates of the North Atlantic minke whale (Balaenoptera acutorostrata), which continues to be a food source for people in Greenland and elsewhere. We compared the Hg levels and stable isotopes of major tissues (kidney, liver and muscle) with those of baleen plates to see whether baleen could be used as a biomonitor of variations of Hg intake and diet both between individuals and within individuals over time. Mercury was significantly correlated with concentrations in all tissues (kidney, liver and muscle). Stable C and N isotopes in baleen were generally similar to those of muscle, which reflects the recent (approximately one month) feeding of the whale, but in some individuals there were significant differences between baleen and muscle. Sectioning of baleen into 1 cm longitudinal increments showed that these differences were due to marked dietary shifts by some individuals over time that had been recorded in the baleen but were lost from the muscle record. Whole baleen C and N isotopes were better correlated with tissue Hg levels, suggesting that baleen may provide a more reliable indicator of long-term average diet, which in turn may be better related to Hg accumulation in tissues than the shorter-term diet record contained in muscle.

Tests of the fidelity of lake sediment core records of mercury deposition to known histories of mercury contamination.

There has been recent controversy over the discrimination between natural and anthropogenic loadings of mercury to lakes. Sediment core profiles have been interpreted as evidence that inputs to lakes have increased. Some investigators have argued, however, that mercury may be sufficiently mobile in sediments to generate profiles that are misinterpreted as historical records. This argument can be tested where the histories of inputs of mercury are known independently from other kinds of information. We have such cases in Canadian lakes and we have been able to assemble sediment core records for comparison with known source histories. Three cases are represented by Clay Lake in Ontario where the source was a chlor-alkali plant with a known history of mercury discharges, Giauque Lake in the Northwest Territories where mercury was used at a gold mine to extract gold from ore, and Stuart Lake in British Columbia where a mercury mine operated for a known period at Pinchi Lake, the lake immediately upstream from Stuart Lake. In these cases lake sediment cores were dated using lead-210 and cesium-137 and then slices were analysed for mercury. The histories of mercury deposition derived from the cores agreed well with the known histories of inputs.

Micro-spatial variations of heavy metals in the teeth of walrus as determined by laser ablation ICP-MS: the potential for reconstructing a history of metal exposure.

This study explored the possibility of using laser ablation inductively-coupled plasma-mass spectroscopy to measure trace metals and other elements within the annual growth layers of the teeth of walrus harvested from the Canadian Arctic. Using sample ablation "footprints" of 125 microns diameter on transects across the exposed cross-sections of teeth, this technique detected Pb, Cu, Zn and Sr, but not Cd, in tooth cementum. The micro-spatial patterns of elements were consistent among different transects on the same tooth, and revealed subtle differences between animals of different ages. The youngest walrus in the sample (4 yr) contained higher concentrations of Pb and Cu than older animals in the growth layer deposited during the first year of life, while the oldest animal (33 yr) exhibited higher Pb and Zn than younger animals in the outer layer corresponding to the year 1988. The differences between animals and across annual layers may reflect both life history and metal exposure phenomena, including high amounts of metals transferred from mothers to pups in maternal milk. The ability to detect metals in a repeatable fashion within annual growth layers suggests that metal exposure histories accurate to within a year might be re-constructed for the life-times of long-lived animals, and that a series of such individual studies would allow exposure histories covering centuries to be quickly assembled. These data may suggest the most likely explanation for the currently high levels of some metals observed in certain Arctic marine mammals, i.e., natural phenomenon or anthropogenic contamination.

Bioaccumulation and toxicology of chromium: implications for wildlife.

The major source of exposure to Cr for wild birds and mammals is through ingestion with food. Chromium(VI) compounds are absorbed significantly more efficiently (2-10% of dose) from the GI tract than inorganic Cr(III) compounds (0.5-3%), due to the increased membrane permeability of the former. Transfer of Cr(VI) into mammalian fetuses has been documented at oral doses of 500 mg Cr/L in drinking water, and injected single doses of 5 mg Cr(VI)/kg BW in dams were teratogenic. Cr concentration data for mammalian and avian wildlife species and their potential food organisms are scarce. Worldwide, fewer than 50 species of free-living mammals and birds have been surveyed with regard to tissue Cr concentrations. Tissue concentrations in animals living in habitats remote from sources of Cr contamination range from approximately 0.1-15 micrograms/g DW depending on the species and tissue analyzed. In habitats experiencing Cr pollution, levels can be up to two orders of magnitude higher. Eisler (1986) suggested that tissue concentrations in wildlife > 4 micrograms/g DW be considered to indicate likely contamination by Cr. Bone tissue often accumulates higher concentrations than other tissues in animals chronically exposed to Cr. Measuring concentrations only in the liver and/or kidneys has been a common practice, yet these organs failed to show evidence of extant Cr contamination in some cases. It is recommended that analysis of the bone, liver, and kidneys be a minimum requirement for future Cr biomonitoring studies. Concentrations in fur or feathers can be extremely variable even among individuals within the same habitat. At best, concentrations in fur and feathers might be used to indicate relative levels of airborne Cr contamination. The toxicological significance of "elevated" Cr concentrations is largely unknown because toxicological data on free-living wildlife species are virtually nonexistent. Based on controlled dosing studies in which Cr compounds were administered orally to experimental animals, dietary Cr concentrations > or = 10 micrograms/g DW in food should be considered potentially harmful to the health and reproductive success of wildlife consumers. Certain species of fish and aquatic invertebrates are sensitive to Cr, showing reduced survival or growth at Cr(VI) concentrations > 10 micrograms/L. The elimination of these organisms from environments contaminated with Cr may have detrimental effects on wild birds and mammals that depend on such organisms for food.(ABSTRACT TRUNCATED AT 400 WORDS)

Changes in metal-binding peptides due to acclimation to cadmium transferred between ramets of Salvinia minima.

Different ramets of a clonal plant exploiting a patchily metal-contaminated habitat may be exposed to different levels of toxic metals. This study investigated whether the exposure of older ("parent") ramets to Cd affected the levels of metal-binding peptides and essential elements in younger ("daughter") ramets which were not exposed to ambient Cd. Pre-treatment of parent ramets of Salvinia minima with 50 µg Cd·l-1 increased the levels of thiols and phytochelatins (PCs), decreased Mg and increased Cu, Zn and S in daughter ramets growing in a Cd-free medium. Acclimation of parents to lower Cd levels (10 and 25 µg Cd·l-1) increased thiols and decreased cysteine and glutathione in daughters, but did not increase PCs. Parental acclimation to all Cd concentrations tested reduced PC production in daughter ramets during subsequent Cd exposure. Daughter ramets from parents pre-treated with 25 µg Cd·l-1 were more Cd tolerant than controls. Although the tolerant daughters contained 35% more thiols than controls, fractionation of tissue Cd showed no difference between the control and tolerant ramets in the fraction of Cd bound by thiol compounds. Thus, while the acclimation of parent plants to Cd increased levels of metal-binding peptides and thiols in daughter ramets, the relationship between these compounds and the Cd tolerance of daughters is unclear.