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Abstract: The aging of “new” mercury (Hg) was investigated in Experimental Lake 658 as part of the Mercury Experiment To Assess Atmospheric Loading In Canada and the United States (METAALICUS). Mercury enriched in 202Hg was added to the epilimnion over a three-year period to simulate direct atmospheric deposition. We evaluated the aging of newly added mercury (HgLake) in the water column using chemical methods and experiments to examine differences in phase partitioning and transport compared to the ambient pool, HgAmb. Aging was sufficiently slow to observe differences in the partitioning characteristics of HgLake and HgAmb. Amended HgLake initially partitioned to a greater extent to epilimnetic particulate matter (log Kd of HgLake =5.08; log Kd of HgAmb =4.9). HgLake was transported rapidly to the hypolimnion by settling particulate matter. Partitioning became more similar after amended Hg was recycled within the hypolimnion through redox processes. Experiments showed the removal of Hg from the aqueous phase by Fe and/or Mn oxyhydroxide–organic matter complexes. Separations using the anion exchange resin DEAE indicated that both HgLake and HgAmb were associated mainly with dissolved organic matter (DOM) and with partial association with sulfide in anoxic waters, but the degree of association of HgLake with DOM was higher in oxic (epilimnetic) waters. In the solid phase, chemical fractionation indicated greater association of HgLake with organic matter, while HgAmb showed greater association with oxyhydroxide and inert phases. Overall, the results suggest that “new” Hg added from the atmosphere is initially more particle-reactive than ambient Hg in the epilimnion, where initial sorption/partitioning occurs mainly to plankton and detrital particles. Once Hg has been deposited at the sediment–water interface, extended equilibration time in combination with microbial and chemical redox processes “age” the “new” Hg, and particle partitioning becomes similar for the added isotope and ambient pools. [Copyright &y& Elsevier]

Although lead isotope ratios have been used to identify lead ammunition (lead shotshell pellets and bullets) as a source of exposure for First Nations people of Canada, the actual source of lead exposure needs to be further clarified. Whole blood samples for First Nations people of Ontario, Canada, were collected from participants prior to the traditional spring harvest of water birds, as well as post-harvest. Blood-lead levels and stable lead isotope ratios prior to, and after the harvest were determined by ICP-MS. Data were analyzed by paired t-tests and Wilcoxon Signed-Ranks tests. All participants consumed water birds harvested with lead shotshell during the period of study. For the group excluding six males who were potentially exposed to other sources of lead (as revealed through a questionnaire), paired t-tests and Wilcoxon Signed-Ranks tests showed consistent results: significant (p <0.05) increases in blood-lead concentrations and blood levels of 206Pb/204Pb and 206Pb/207Pb towards the mean values we previously reported for lead shotshell pellets; and a significant decrease in 208Pb/206Pb values towards the mean for lead shotshell pellets. However, when we categorized the group further into a group that did not use firearms and did not eat any other traditional foods harvested with lead ammunition other than waterfowl, our predictions for 206Pb/204Pb, 206Pb/207Pb and 208Pb/206Pb hold true, but there was not a significant increase in blood-lead level after the hunt. It appears that the activity of hunting (i.e., use of a shotgun) was also an important route of lead exposure. The banning of lead shotshell for all game hunting would eliminate a source of environmental lead for all people who use firearms and/or eat wild game. [Copyright &y& Elsevier]

Abstract: 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 δ 15N values: 15.6–20.5‰) than modern animals (δ 15N: 17.2–21.1‰). 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 δ 13C 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. [Copyright &y& Elsevier]

Migratory songbirds breeding in the Canadian Boreal forest are exposed to mercury (Hg), a potent neurotoxin that impairs avian health, however, the degree of exposure depends on many factors. As breeding grounds are geographically remote and vast, the measurement of Hg in individual birds is impractical particularly at large spatial scales. Here, we present a Canada-wide dataset of nearly 2000 migratory songbirds that were used to assess summer Hg exposure of 15 songbird species sampled during fall migration. We measured Hg concentrations in tail feathers and related those to dietary guild, geographic capture location, age, sex and probable breeding ground locations using feather δ 2 H. Overall mean (±SE) feather Hg concentration was 1.49 ± 0.03 μg/g (N = 1946): however, a clear geographic gradient in feather Hg concentrations emerged being highest in East and lowest in West. Dietary guild was the next strongest predictor of feather Hg with insectivorous songbirds in Eastern Canada at particular risk due to Hg exposure on summer breeding grounds. This broad-scale assessment of Hg exposure in migratory songbirds in Canada can be used to guide future studies on finer-scale determinants of Hg exposure in birds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Mining activities at Duparquet in Western Quebec (Canada) have significantly affected the local environment and left behind significant amounts of metals. Monitoring this contamination is essential to infer its past and present impacts on environmental quality and to evaluate the resulting human exposure. In that context, we measured long time series of Pb concentrations and their corresponding stable isotope ratios in long-lived white cedars (Thuja occidentalis L.) growing at Duparquet Lake in order to evaluate potential time variations of the Pb environmental contamination as well as to identify the responsible source(s). Results show that before 1950, Pb at Duparquet is mostly terrigenous. Lead concentrations rapidly increase afterwards. A simultaneous shift to lower 206 Pb/ 207 Pb ratios identifies the smelting of Abitibi ores as the source of contamination. An isotope mass balance model evaluates at roughly 7.5-20%, 5-40%, 5-9% and <3% the Pb contributions from local smelters at distances of 3.6, 3.9, 7 and 9 km, respectively. The dispersion of the Pb contamination plume is possibly driven by the distance from the Beattie smelter. We finally estimated a delay of at least 13 years between atmospheric emissions from the Beattie smelting activities and the time they are recorded by tree rings. Ultimately, this study demonstrates that white cedar tree rings series provide reliable archives of past and present Pb atmospheric contamination., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

To evaluate metallurgical processing as a source of Zn and Cd isotopic fractionation and to potentially trace their distribution in the environment, high-precision MC-ICP-MS Zn, Cd and Pb isotope ratio measurements were made for samples from the integrated Zn-Pb smelting and refining complex in Trail, B.C., Canada. Significant fractionation of Zn and Cd isotopes during processing of ZnS and PbS ore concentrates is demonstrated by the total variation in delta(66/64)Zn and delta(114/110)Cd values of 0.42 per thousand and 1.04 per thousand, respectively, among all smelter samples. No significant difference is observed between the isotopic compositions of the Zn ore concentrates (delta(66/64)Zn=0.09 to 0.17 per thousand; delta(114/110)Cd=-0.13 to 0.18 per thousand) and the roasting product, calcine (delta(66/64)Zn=0.17 per thousand; delta(114/110)Cd=0.05 per thousand), due to approximately 100% recovery from roasting. The overall Zn recovery from metallurgical processing is approximately 98%, thus the refined Zn metal (delta(66/64)Zn=0.22 per thousand) is not significantly fractionated relative to the starting materials despite significantly fractionated fume (delta(66/64)Zn=0.43 per thousand) and effluent (delta(66/64)Zn=0.41 to 0.51 per thousand). Calculated Cd recovery from metallurgical processing is 72-92%, with the majority of the unrecovered Cd lost during Pb operations (delta(114/110)Cd=-0.38 per thousand). The refined Cd metal is heavy (delta(114/110)Cd=0.39 to 0.52 per thousand) relative to the starting materials. In addition, significant fractionation of Cd isotopes is evidenced by the relatively light and heavy isotopic compositions of the fume (delta(114/110)Cd=-0.52 per thousand) and effluent (delta(114/110)Cd=0.31 to 0.46 per thousand). In contrast to Zn and Cd, Pb isotopes are homogenized by mixing during processing. The total variation observed in the Pb isotopic compositions of smelter samples is attributed to mixing of ore sources with different radiogenic signatures., (Copyright 2010 Elsevier B.V. All rights reserved.)

Concentrations and stable isotope ratios of lead (Pb) from lake sediments were used to quantify temporal patterns of anthropogenic Pb pollution in the Clyde River region of Baffin Island, Arctic Canada. Surface sediments from eight lakes on eastern Baffin Island and one from northern-most Greenland, spanning a gradient of 20 degrees latitude, showed great variability with respect to Pb concentration and stable isotopic Pb ratios, with little apparent latitudinal trend. To constrain the temporal evolution of regional Pb pollution, a well-dated core from one of the sites, Lake CF8 on east-central Baffin Island, was analyzed geochemically at high stratigraphic resolution. A pronounced decrease in the (206)Pb/(207)Pb ratio occurs in sediments deposited between 1923 and the mid-1970s, likely reflecting alkyl-Pb additives derived from the combustion of fossil fuels at a global scale. A two-component mixing model indicates that 17-26% of the Pb in the labile fraction of sediments deposited in Lake CF8 between 2001 and 2005 is from anthropogenic input. A Pb-Pb co-isotopic plot ((206)Pb/(207)Pb vs.(208)Pb/(206)Pb ratios) of the Lake CF8 time series data indicates multiple possible sources of industrial Pb pollution. Despite widespread reductions in industrial Pb emissions since the 1970s, there is no evidence for attendant reductions of pollution Pb at Lake CF8. Enhanced scavenging from increased primary production as well as changing precipitation rates as climate warms may represent important factors that modulate Pb deposition to Lake CF8, and Arctic lakes elsewhere.