P.M. Outridge

A mass balance inventory of mercury in the Arctic Ocean

Environmental context. Mercury (Hg) occurs at high concentrations in Arctic marine wildlife, posing a possible health risk to northern peoples who use these animals for food. We find that although the dramatic Hg increases in Arctic Ocean animals since pre-industrial times can be explained by sustained small annual inputs, recent rapid increases probably cannot, because of the existing large oceanic Hg reservoir (the ‘flywheel’ effect). Climate change is a possible alternative force underpinning recent trends. Abstract. The present mercury (Hg) mass balance was developed to gain insights into the sources, sinks and processes regulating biological Hg trends in the Arctic Ocean. Annual total Hg inputs (mainly wet deposition, coastal erosion, seawater import, and ‘excess’ deposition due to atmospheric Hg depletion events) are nearly in balance with outputs (mainly shelf sedimentation and seawater export), with a net 0.3% year–1 increase in total mass. Marine biota represent a small fraction of the ocean’s existing total Hg and methyl-Hg (MeHg) inventories. The inertia associated with these large non-biological reservoirs means that ‘bottom-up’ processes (control of bioavailable Hg concentrations by mass inputs or Hg speciation) are probably incapable of explaining recent biotic Hg trends, contrary to prevailing opinion. Instead, varying rates of bioaccumulation and trophic transfer from the abiotic MeHg reservoir may be key, and are susceptible to ecological, climatic and biogeochemical influences. Deep and sustained cuts to global anthropogenic Hg emissions are required to return biotic Hg levels to their natural state. However, because of mass inertia and the less dominant role of atmospheric inputs, the decline of seawater and biotic Hg concentrations in the Arctic Ocean will be more gradual than the rate of emission reduction and slower than in other oceans and freshwaters. Climate warming has likely already influenced Arctic Hg dynamics, with shrinking sea-ice cover one of the defining variables. Future warming will probably force more Hg out of the ocean’s euphotic zone through greater evasion to air and faster Hg sedimentation driven by higher primary productivity; these losses will be countered by enhanced inputs from coastal erosion and rivers.

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.

Anthropogenic contributions to mercury levels in present-day Arctic animals—A review

BACKGROUND Because of concern about the recently increasing levels of biological Hg in some areas of the Arctic, we examined the literature concerning the long-term changes of Hg in humans and selected Arctic marine mammals and birds of prey since pre-industrial times (i.e. before 1800A.D.), to determine the anthropogenic contribution to present-day Hg concentrations and the historical timing of any changes. METHODS Mercury data from published articles were extracted on historical and pre-industrial concentrations as percentages of the recent maximum, as well as the man-made contribution was calculated and depicted in a uniform manner to provide an overview of the development over time. RESULTS AND DISCUSSION Trends of [Hg] in hard tissues such as teeth, hair and feathers consistently showed that there had been an order-of-magnitude increase of [Hg] in Arctic marine foodweb-based animals that began in the mid- to late-19th Century and accelerated in the 20th Century. The median man-made contribution to present-day Hg concentrations was 92.4% ranging from 74.2 to 94.4%. Confidence in our data was increased by accompanying data in some studies on stable isotopes (delta(13)C, delta(15)N), which allowed us to normalize where necessary for changes in animal trophic position and feeding location over time, and by careful attention to the possibility of sample chemical diagenesis (Hg contamination or loss) which can alter the Hg content of ancient hard tissues. CONCLUSIONS Wildlife hard tissue matrices provide consistent information with respect to the steep onset of Hg exposure of Arctic wildlife beginning in the latter half of the 19th Century. Today the man-made contribution was found to be above 92%. Stable isotope analyses provide important information to normalize for possible changes in diet over time, and are highly relevant to include when interpreting temporal trends, baseline concentrations as well as man-made anthropogenic contribution of Hg.

How does climate change influence arctic mercury

Recent studies have shown that climate change is already having significant impacts on many aspects of transport pathways, speciation and cycling of mercury within Arctic ecosystems. For example, the extensive loss of sea-ice in the Arctic Ocean and the concurrent shift from greater proportions of perennial to annual types have been shown to promote changes in primary productivity, shift foodweb structures, alter mercury methylation and demethylation rates, and influence mercury distribution and transport across the ocean-sea-ice-atmosphere interface (bottom-up processes). In addition, changes in animal social behavior associated with changing sea-ice regimes can affect dietary exposure to mercury (top-down processes). In this review, we address these and other possible ramifications of climate variability on mercury cycling, processes and exposure by applying recent literature to the following nine questions; 1) What impact has climate change had on Arctic physical characteristics and processes? 2) How do rising temperatures affect atmospheric mercury chemistry? 3) Will a decrease in sea-ice coverage have an impact on the amount of atmospheric mercury deposited to or emitted from the Arctic Ocean, and if so, how? 4) Does climate affect air-surface mercury flux, and riverine mercury fluxes, in Arctic freshwater and terrestrial systems, and if so, how? 5) How does climate change affect mercury methylation/demethylation in different compartments in the Arctic Ocean and freshwater systems? 6) How will climate change alter the structure and dynamics of freshwater food webs, and thereby affect the bioaccumulation of mercury? 7) How will climate change alter the structure and dynamics of marine food webs, and thereby affect the bioaccumulation of marine mercury? 8) What are the likely mercury emissions from melting glaciers and thawing permafrost under climate change scenarios? and 9) What can be learned from current mass balance inventories of mercury in the Arctic? The review finishes with several conclusions and recommendations.

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.

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.

Population substructure of North Atlantic minke whales (Balaenoptera acutorostrata) inferred from regional variation of elemental and stable isotopic signatures in tissues

Abstract Information on population structure is essential for estimating population demographics and managing the impacts of exploitation of North Atlantic minke whales ( Balaenoptera acutorostrata ). New approaches including assessment of geochemical signatures in tissues can assist in defining such structure. This study determined regional variations in long-term elemental diagnostics of stock differences among 159 minke whales harvested in West Greenland, the Northeast Atlantic Ocean and the North Sea in 1998. The diagnostics tested included mercury (Hg), selenium (Se) and cadmium (Cd) in various tissues, and the trace and major element composition of baleen. Supporting data was also gathered on δ 15 N and δ 13 C and stable lead isotope ratios. For female whales, significant differences in at least one long-term diagnostic element occurred between several areas. Existence of the following population substructure was inferred: (a) West Greenland, (b) a central group represented by whales from Jan Mayen, (c) a northeastern stock encompassing the Barents Sea, Svalbard and coastal Norway, and (d) the North Sea. These groups were consistent with those defined genetically by Andersen et al. [Mar. Ecol., Prog. Ser. 247 (2003) 263]. Males appeared to fall into similar groupings to females but because of smaller sample sizes fewer significant differences occurred between areas. Stable-isotopic values in minke whales suggested lower trophic-level feeding in this species than hitherto suspected, with significant dietary differences between areas. Variations in feeding habits appeared to explain part of the geographical variation in tissue Cd, but not tissue Hg or Se. Differences among elements with a relatively long biological half-life in specific tissues suggested that groups of minke whales have fidelity to certain summer feeding areas at least for several years.

Mercury–organic matter relationships in pre-pollution sediments of thermokarst lakes from the Mackenzie River Delta, Canada: the role of depositional environment

This study investigates the influence of organic matter (OM) on the historical variations of Hg in sediments from two closely-situated Canadian Arctic lakes, prior to the advent of Hg pollution inputs. Because of variable landscape evolution in the Mackenzie River Delta over the past 1–3 millennia, the lakes provide distinctly different histories of OM sources, types, and degree of aquatic productivity (i.e., depositional environments). They also differ significantly in their pre-1900 Hg concentration profiles. When labile, kerogen-like carbon (“S2”) from aquatic sources (diatoms and other unicellular algae) increased between 750 and 1900 A.D. in the more productive lake (Nesbitt), Hg concentrations also increased by ca. 50%. In contrast, S2 carbon concentrations in the nearby organic-poor lake (Big Lake) were several-times lower than in Nesbitt and decreased over the past millennium, while Hg concentrations showed no trend probably reflecting the stable input of clastic material from tundra soils. The contrast between lakes suggests that OM derived from unicellular algae is more effective at scavenging Hg than OM from terrestrial plants or aquatic macrophytes, possibly because of a higher content of labile, sulphur-rich compounds, high particle surface area and its dispersion throughout the water column. The results indicate that, in the absence of anthropogenic Hg inputs, increasing phytoplankton productivity and Hg scavenging alone can lead to significant increases in the Hg content of lake sediments. This finding is consistent with the hypothesis that increasing lake productivity because of climate warming during the twentieth century has confounded the interpretation of recently increasing Hg levels in northern lake sediments as being unequivocally due to anthropogenic Hg deposition. This study also suggests that sedimentary TOC by itself is a poor and sometimes misleading indicator of possible changes in the source and quality of OM in aquatic systems, which can have a major impact on Hg concentrations in sediments.

Indication of two Pacific walrus stocks from whole tooth elemental analysis

The Pacific walrus (Odobenus rosmarus divergens) is considered to be a single panmictic population for management purposes. However, studies on population structuring in this species are limited; in part, because portions of the population’s range are often inaccessible. Therefore, alternative and complementary methods for investigating stock structure in the Pacific walrus are of particular interest. We used measures of elemental concentrations in whole tooth sections from ICP-MS in a discriminant analysis to investigate evidence of stock separation between walruses from two of three known breeding areas (S.E. Bering, St Lawrence, and Anadyr Gulf). Elemental compositions of teeth from female and male walruses from the S.E. Bering and St Lawrence breeding areas were significantly different, providing evidence of separate stocks. We also obtained insights into the potential relation of walruses from non-breeding areas to walruses from these breeding groups based on similarities in their dental elemental profiles.

Toward an assessment of the global inventory of present-day mercury releases to freshwater environments

Aquatic ecosystems are an essential component of the biogeochemical cycle of mercury (Hg), as inorganic Hg can be converted to toxic methylmercury (MeHg) in these environments and reemissions of elemental Hg rival anthropogenic Hg releases on a global scale. Quantification of effluent Hg releases to aquatic systems globally has focused on discharges to the global oceans, rather than contributions to freshwater systems that affect local exposures and risks associated with MeHg. Here we produce a first-estimate of sector-specific, spatially resolved global aquatic Hg discharges to freshwater systems. We compare our release estimates to atmospheric sources that have been quantified elsewhere. By analyzing available quantitative and qualitative information, we estimate that present-day global Hg releases to freshwater environments (rivers and lakes) associated with anthropogenic activities have a lower bound of ~1000 Mg·a−1. Artisanal and small-scale gold mining (ASGM) represents the single largest source, followed by disposal of mercury-containing products and domestic waste water, metal production, and releases from industrial installations such as chlor-alkali plants and oil refineries. In addition to these direct anthropogenic inputs, diffuse inputs from land management activities and remobilization of Hg previously accumulated in terrestrial ecosystems are likely comparable in magnitude. Aquatic discharges of Hg are greatly understudied and further constraining associated data gaps is crucial for reducing the uncertainties in the global biogeochemical Hg budget.