Mercury Isotope Variations in Lake Sediment Cores in Response to Direct Mercury Emissions from Non-Ferrous Metal Smelters and Legacy Mercury Remobilization.

Nature archives record atmospheric mercury (Hg) depositions from directly emitted Hg and re-emitted legacy Hg. Tracing the legacy versus newly deposited Hg is still, however, challenging. Here, we measured Hg isotope compositions in three dated sediment cores at different distances from the Flin Flon smelter, the largest Canadian Hg sources to the atmosphere during the 1930s-2000s. During the smelter's operative period, Hg isotope compositions showed limited variations in the near-field lake (<10 km) sediments but were rather variable in middle- (20-75 km) and far-field lake (∼800 km) sediments. Only the post-2000 sediments in middle/far-field lakes showed significantly negative Hg isotope shifts, while sediments from the 1970s-1990s had Hg isotope values resembling those of near-field lake post-1930 sediments. We suggest that the smelter's peak Hg emissions during the 1970s-1990s, which coincided with the deployment of a super stack in the mid-1970s, largely increased the long-range dispersion of smelter plumes. For the top post-2000 sediments, the fugitive dust from ore tailings and terrestrial legacy Hg re-emissions dominated Hg deposition in near-field lakes and middle/far-field lakes, respectively. Our study demonstrates that legacy Hg remobilization now exports substantial amounts of Hg to ecosystems, highlighting the need for aggressive remediation measures of Hg-contaminated sites.

Quantification of Spatial and Temporal Trends in Atmospheric Mercury Deposition across Canada over the Past 30 Years.

Mercury (Hg) is a pollutant of concern across Canada and transboundary anthropogenic Hg sources presently account for over 95% of national anthropogenic Hg deposition. This study applies novel statistical analyses of 82 high-resolution dated lake sediment cores collected from 19 regions across Canada, including nearby point sources and in remote regions and spanning a full west-east geographical range of ∼4900 km (south of 60°N and between 132 and 64°W) to quantify the recent (1990-2018) spatial and temporal trends in anthropogenic atmospheric Hg deposition. Temporal trend analysis shows significant synchronous decreasing trends in post-1990 anthropogenic Hg fluxes in western Canada in contrast to increasing trends in the east, with spatial patterns largely driven by longitude and proximity to known point source(s). Recent sediment-derived Hg fluxes agreed well with the available wet deposition monitoring. Sediment-derived atmospheric Hg deposition rates also compared well to the modeled values derived from the Hg model, when lake sites located nearby (<100 km) point sources were omitted due to difficulties in comparison between the sediment-derived and modeled values at deposition "hot spots". This highlights the applicability of multi-core approaches to quantify spatio-temporal changes in Hg deposition over broad geographic ranges and assess the effectiveness of regional and global Hg emission reductions to address global Hg pollution concerns.

Accumulating Mercury and Methylmercury Burdens in Watersheds Impacted by Oil Sands Pollution.

Bitumen mining and upgrading in northeastern Alberta, Canada, releases toxic pollutants into the atmosphere, including mercury (Hg) and methylmercury (MeHg). This Hg and MeHg is then deposited to the surrounding landscape; however, the fate of these contaminants remains unknown. Here, we compare snowpack chemistry to high-frequency measurements of river water quality across six watersheds (five impacted by oil sands development and one unimpacted). Catchment scale snowpack Hg and MeHg loads normalized to watershed area were highest near oil sands operations. River water Hg concentrations and loads tracked discharge and tended to be higher downstream of mining operations, while MeHg concentrations and loads increased through the summer, reflecting peak summer MeHg production rates. Except in the reference watershed, snowpack Hg and MeHg loads equaled or exceeded the amount of Hg and MeHg exported during freshet and, in some cases, the entire hydrologic year. This suggests landscapes across the oil sands region, which are dominated by low-relief wetlands and other shallow-water systems, are accumulating Hg and MeHg. Importantly, during years of high discharge, these low-relief systems appear to become better connected and flush MeHg (and Hg) from the watershed. Thus, these watersheds may act as temporary, rather than as permanent, natural repositories of oil sands contaminants.

Deposition and Source Identification of Nitrogen Heterocyclic Polycyclic Aromatic Compounds in Snow, Sediment, and Air Samples from the Athabasca Oil Sands Region.

Polycyclic aromatic compounds (PACs) can have multiple sources in the Athabasca Oil Sands Region (AOSR). The current study was designed to identify and explore the potential of nitrogen heterocyclic PACs (NPACs) as source indicators in snowpack, lake sediment and passive air samples from the AOSR during 2014-2015. Source samples including petroleum coke (petcoke), haul road dust, and unprocessed oil sands were also analyzed. Samples were analyzed using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry, and liquid chromatography-high resolution Orbitrap mass spectrometry. Over 200 NPACs were identified and classified into at least 24 isomer groups, including alkylated carbazoles, benzocarbazoles, and indenoquinolines. Levels of NPACs in environmental samples decreased with distance from the main developments and with increasing depth in lake sediments but were detected within 50 km from the major developments. The composition profiles of several NPAC isomer classes, such as dimethylcarbazoles, showed that petcoke had a distinct distribution of NPACs compared to the haul road dust and unprocessed oil sands ores and was the most similar source material to near-field environmental samples. These results suggest that petcoke is a major contributing source for the identified NPACs and that these compounds have the potential to be used as source indicators for future research in the AOSR.

Sources of Methylmercury to Snowpacks of the Alberta Oil Sands Region: A Study of In Situ Methylation and Particulates.

Snowpacks in the Alberta Oil Sands Region (AOSR) of Canada contain elevated loadings of methylmercury (MeHg; a neurotoxin that biomagnifies through foodwebs) due to oil sands related activities. At sites ranging from 0 to 134 km from the major AOSR upgrading facilities, we examined sources of MeHg by quantifying potential rates of MeHg production in snowpacks and melted snow using mercury stable isotope tracer experiments, as well as quantifying concentrations of MeHg on particles in snowpacks (pMeHg). At four sites, methylation rate constants were low in snowpacks (km = 0.001-0.004 d-1) and nondetectable in melted snow, except at one site (km = 0.0007 d-1). The ratio of methylation to demethylation varied between 0.3 and 1.5, suggesting that the two processes are in balance and that in situ production is unlikely an important net source of MeHg to AOSR snowpacks. pMeHg concentrations increased linearly with distance from the upgraders (R2 = 0.71, p < 0.0001); however, snowpack total particle and pMeHg loadings decreased exponentially over this same distance (R2 = 0.49, p = 0.0002; R2 = 0.56, p < 0.0001). Thus, at near-field sites, total MeHg loadings in snowpacks were high due to high particle loadings, even though particles originating from industrial activities were not MeHg rich compared to those at remote sites. More research is required to identify the industrial sources of snowpack particles in the AOSR.

Widespread Atmospheric Tellurium Contamination in Industrial and Remote Regions of Canada.

High tech applications, primarily photovoltaics, have greatly increased demand for the rare and versatile but toxic element tellurium (Te). Here we examine dated lake sediment Te concentration profiles collected near potential point sources (metal smelters, coal mining/combustion facilities, oil sands operations) and from rural regions and remote natural areas of Canada. Te contamination was most prevalent near a Cu/Zn smelter where observed deposition infers 21 g Te released per metric ton (t) of Cu processed. Globally, 9,500 t is predicted to have been atmospherically deposited near Cu smelters post-1900. In a remote area of central Canada (Experimental Lakes Area; ELA), preindustrial Te deposition rates were equivalent to the estimated average global mass flux supplied from natural sources; however more surprisingly, modern Te deposition rates were 6-fold higher and comparable with Te measurements in precipitation. We therefore suggest that sediment cores reliably record atmospheric Te deposition and that anthropogenic activities have significantly augmented atmospheric Te levels, making it an emerging contaminant of potential concern. Lake water residence time was found to influence lake sediment Te inventories among lakes within a region. The apparent settling rate for Te was comparable to macronutrients (C, N, P), likely indicative of significant biological processing of Te.

A Critical Time for Mercury Science to Inform Global Policy.

Mercury is a global pollutant released into the biosphere by varied human activities including coal combustion, mining, artisanal gold mining, cement production, and chemical production. Once released to air, land and water, the addition of carbon atoms to mercury by bacteria results in the production of methylmercury, the toxic form that bioaccumulates in aquatic and terrestrial food chains resulting in elevated exposure to humans and wildlife. Global recognition of the mercury contamination problem has resulted in the Minamata Convention on Mercury, which came into force in 2017. The treaty aims to protect human health and the environment from human-generated releases of mercury curtailing its movement and transformations in the biosphere. Coincident with the treaty's coming into force, the 13th International Conference of Mercury as a Global Pollutant (ICMGP-13) was held in Providence, Rhode Island USA. At ICMGP-13, cutting edge research was summarized and presented to address questions relating to global and regional sources and cycling of mercury, how that mercury is methylated, the effects of mercury exposure on humans and wildlife, and the science needed for successful implementation of the Minamata Convention. Human activities have the potential to enhance mercury methylation by remobilizing previously released mercury, and increasing methylation efficiency. This synthesis concluded that many of the most important factors influencing the fate and effects of mercury and its more toxic form, methylmercury, stem from environmental changes that are much broader in scope than mercury releases alone. Alterations of mercury cycling, methylmercury bioavailability and trophic transfer due to climate and land use changes remain critical uncertainties in effective implementation of the Minamata Convention. In the face of these uncertainties, important policy and management actions are needed over the short-term to support the control of mercury releases to land, water and air. These include adequate monitoring and communication on risk from exposure to various forms of inorganic mercury as well as methylmercury from fish and rice consumption. Successful management of global and local mercury pollution will require integration of mercury research and policy in a changing world.

Legacy of a half century of Athabasca oil sands development recorded by lake ecosystems.

The absence of well-executed environmental monitoring in the Athabasca oil sands (Alberta, Canada) has necessitated the use of indirect approaches to determine background conditions of freshwater ecosystems before development of one of the Earth's largest energy deposits. Here, we use highly resolved lake sediment records to provide ecological context to ∼50 y of oil sands development and other environmental changes affecting lake ecosystems in the region. We show that polycyclic aromatic hydrocarbons (PAHs) within lake sediments, particularly C1-C4-alkylated PAHs, increased significantly after development of the bitumen resource began, followed by significant increases in dibenzothiophenes. Total PAH fluxes in the modern sediments of our six study lakes, including one site ∼90 km northwest of the major development area, are now ∼2.5-23 times greater than ∼1960 levels. PAH ratios indicate temporal shifts from primarily wood combustion to petrogenic sources that coincide with greater oil sands development. Canadian interim sediment quality guidelines for PAHs have been exceeded since the mid-1980s at the most impacted site. A paleoecological assessment of Daphnia shows that this sentinel zooplankter has not yet been negatively impacted by decades of high atmospheric PAH deposition. Rather, coincident with increases in PAHs, climate-induced shifts in aquatic primary production related to warmer and drier conditions are the primary environmental drivers producing marked daphniid shifts after ∼1960 to 1970. Because of the striking increase in PAHs, elevated primary production, and zooplankton changes, these oil sands lake ecosystems have entered new ecological states completely distinct from those of previous centuries.

Atmospheric deposition of mercury and methylmercury to landscapes and waterbodies of the Athabasca oil sands region.

Atmospheric deposition of metals originating from a variety of sources, including bitumen upgrading facilities and blowing dusts from landscape disturbances, is of concern in the Athabasca oil sands region of northern Alberta, Canada. Mercury (Hg) is of particular interest as methylmercury (MeHg), a neurotoxin which bioaccumulates through foodwebs, can reach levels in fish and wildlife that may pose health risks to human consumers. We used spring-time sampling of the accumulated snowpack at sites located varying distances from the major developments to estimate winter 2012 Hg loadings to a ∼20 000 km(2) area of the Athabasca oil sands region. Total Hg (THg; all forms of Hg in a sample) loads were predominantly particulate-bound (79 ± 12%) and increased with proximity to major developments, reaching up to 1000 ng m(-2). MeHg loads increased in a similar fashion, reaching up to 19 ng m(-2) and suggesting that oil sands developments are a direct source of MeHg to local landscapes and water bodies. Deposition maps, created by interpolation of measured Hg loads using geostatistical software, demonstrated that deposition resembled a bullseye pattern on the landscape, with areas of maximum THg and MeHg loadings located primarily between the Muskeg and Steepbank rivers. Snowpack concentrations of THg and MeHg were significantly correlated (r = 0.45-0.88, p < 0.01) with numerous parameters, including total suspended solids (TSS), metals known to be emitted in high quantities from the upgraders (vanadium, nickel, and zinc), and crustal elements (aluminum, iron, and lanthanum), which were also elevated in this region. Our results suggest that at snowmelt, a complex mixture of chemicals enters aquatic ecosystems that could impact biological communities of the oil sands region.

Mercury biomagnification through food webs is affected by physical and chemical characteristics of lakes.

Mercury (Hg) contamination in aquatic systems remains a global concern because the organic form, methyl Hg (MeHg), can biomagnify to harmful concentrations in fish, fish-eating wildlife, and humans. Food web transfer of MeHg has been explored using models of log MeHg versus relative trophic position (nitrogen isotopes, δ(15)N), but regression slopes vary across systems for unknown reasons. In this study, MeHg biomagnification was determined for 11 lake food webs in Kejimkujik National Park, Nova Scotia, Canada, and compared to physical and chemical lake characteristics using principal component and multiple regression analyses. MeHg biomagnification (regression slopes of log MeHg versus baseline-adjusted δ(15)N for fishes and invertebrates) varied significantly across lakes and was higher in systems with lower aqueous nutrient/MeHg/chloride scores. This is one of the largest, consistent data sets available on MeHg biomagnification through temperate lake food webs and the first study to use a principal component and multiple regression approach to understand how lake chemical and physical characteristics interact to affect biomagnification among systems. Overall, our results show that the magnitude of MeHg biomagnification through lake food webs is related to the chemical and physical characteristics of the systems, but the underlying mechanisms warrant further investigation.

Mercury at the top of the world: A 31-year record of mercury in Arctic char in the largest High Arctic lake, linked to atmospheric mercury concentrations and climate oscillations.

Lake Hazen, the largest lake north of the Arctic circle, is being impacted by mercury (Hg) pollution and climate change. The lake is inhabited by two morphotypes of land-locked Arctic char (Salvelinus alpinus), a sensitive indicator species for pollution and climatic impacts. The objectives of this study were to describe the trends in Hg concentration over time and to determine the relationship of climate to length-at-age and Hg concentrations in each char morphotype, as well as the relationship to atmospheric Hg measurements at a nearby monitoring station. Results for Hg in char muscle were available from 20 sampling years over the period 1990 to 2021. We found significant declines in Hg concentrations for both morphotypes during the 31-year study period. Increased rain and earlier freeze-up of lake ice during the summer growing season was linked to increased length-at-age in both char morphotypes. For the large morphotype, higher total gaseous Hg in the fall and winter seasons was related to higher concentrations of Hg in char, while increased glacial runoff was related to decreases in char Hg. For the small morphotype char, increased snow and snow accumulation in the fall season were linked to declines in char Hg concentration. The Atlantic Multidecadal Oscillation and Arctic Oscillation were positively related to the large char Hg trend and Arctic Oscillation was positively related to the small char Hg trend. Significant trend relationships between atmospheric Hg and Hg in biota in remote regions are rare and uniquely valuable for evaluation of the effectiveness of the Minamata Convention and related monitoring efforts.

Methylmercury cycling in High Arctic wetland ponds: controls on sedimentary production.

Methylmercury (MeHg) is a potent neurotoxin that has been demonstrated to biomagnify in Arctic freshwater foodwebs to levels that may be of concern to Inuit peoples subsisting on freshwater fish, for example. The key process initiating the bioaccumulation and biomagnification of MeHg in foodwebs is the methylation of inorganic Hg(II) to form MeHg, and ultimately how much MeHg enters foodwebs is controlled by the production and availability of MeHg in a particular water body. We used isotopically enriched Hg stable isotope tracers in sediment core incubations to measure potential rates of Hg(II) methylation and investigate the controls on MeHg production in High Arctic wetland ponds in the Lake Hazen region of northern Ellesmere Island (Nunavut, Canada). We show here that MeHg concentrations in sediments are primarily controlled by the sediment methylation potential and the quantity of Hg(II) available for methylation, but not by sediment demethylation potential. Furthermore, MeHg concentrations in pond waters are controlled by MeHg production in sediments, overall anaerobic microbial activity, and photodemethylation in the water column.

Methylmercury cycling in High Arctic wetland ponds: sources and sinks.

The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwebs) to Arctic freshwater organisms have not been clearly identified. We used a mass balance approach to quantify MeHg production in two wetland ponds in the Lake Hazen region of northern Ellesmere Island, NU, in the Canadian High Arctic and to evaluate the importance of these systems as sources of MeHg to Arctic foodwebs. We show that internal production (1.8-40 ng MeHg m(-2) d(-1)) is a much larger source of MeHg than external inputs from direct atmospheric deposition (0.029-0.051 ng MeHg m(-2) d(-1)), as expected. Furthermore, MeHg cycling in these systems is dominated by Hg(II) methylation and MeHg photodemethylation (2.0-33 ng MeHg m(-2) d(-1)), which is a sink for a large proportion of the MeHg produced by Hg(II) methylation in these ponds. We also show that MeHg production in the two study ponds is comparable to what has previously been measured in numerous more southerly systems known to be important MeHg sources, such as temperate wetlands and lakes, demonstrating that wetland ponds in the High Arctic are important sources of MeHg to local aquatic foodwebs.

Mercury in Arctic marine ecosystems: sources, pathways and exposure.

Mercury in the Arctic is an important environmental and human health issue. The reliance of Northern Peoples on traditional foods, such as marine mammals, for subsistence means that they are particularly at risk from mercury exposure. The cycling of mercury in Arctic marine systems is reviewed here, with emphasis placed on the key sources, pathways and processes which regulate mercury levels in marine food webs and ultimately the exposure of human populations to this contaminant. While many knowledge gaps exist limiting our ability to make strong conclusions, it appears that the long-range transport of mercury from Asian emissions is an important source of atmospheric Hg to the Arctic and that mercury methylation resulting in monomethylmercury production (an organic form of mercury which is both toxic and bioaccumulated) in Arctic marine waters is the principal source of mercury incorporated into food webs. Mercury concentrations in biological organisms have increased since the onset of the industrial age and are controlled by a combination of abiotic factors (e.g., monomethylmercury supply), food web dynamics and structure, and animal behavior (e.g., habitat selection and feeding behavior). Finally, although some Northern Peoples have high mercury concentrations of mercury in their blood and hair, harvesting and consuming traditional foods have many nutritional, social, cultural and physical health benefits which must be considered in risk management and communication.

Differences in mercury bioaccumulation between polar bears (Ursus maritimus) from the Canadian high- and sub-Arctic.

Polar bears (Ursus maritimus) are being impacted by climate change and increased exposure to pollutants throughout their northern circumpolar range. In this study, we quantified concentrations of total mercury (THg) in the hair of polar bears from Canadian high- (southern Beaufort Sea, SBS) and sub- (western Hudson Bay, WHB) Arctic populations. Concentrations of THg in polar bears from the SBS population (14.8 ± 6.6 µg g(-1)) were significantly higher than in polar bears from WHB (4.1 ± 1.0 µg g(-1)). On the basis of δ(15)N signatures in hair, in conjunction with published δ(15)N signatures in particulate organic matter and sediments, we estimated that the pelagic and benthic food webs in the SBS are ∼ 4.7 and ∼ 4.0 trophic levels long, whereas in WHB they are only ∼ 3.6 and ∼ 3.3 trophic levels long. Furthermore, the more depleted δ(13)C ratios in hair from SBS polar bears relative to those from WHB suggests that SBS polar bears feed on food webs that are relatively more pelagic (and longer), whereas polar bears from WHB feed on those that are relatively more benthic (and shorter). Food web length and structure accounted for ∼ 67% of the variation we found in THg concentrations among all polar bears across both populations. The regional difference in polar bear hair THg concentrations was also likely due to regional differences in water-column concentrations of methyl Hg (the toxic form of Hg that biomagnifies through food webs) available for bioaccumulation at the base of the food webs. For example, concentrations of methylated Hg at mid-depths in the marine water column of the northern Canadian Arctic Archipelago were 79.8 ± 37.3 pg L(-1), whereas, in HB, they averaged only 38.3 ± 16.6 pg L(-1). We conclude that a longer food web and higher pelagic concentrations of methylated Hg available to initiate bioaccumulation in the BS resulted in higher concentrations of THg in polar bears from the SBS region compared to those inhabiting the western coast of HB.

Climate change and mercury accumulation in Canadian high and subarctic lakes.

Mercury (Hg) profiles were compared to profiles of climate indicators including microfossil remains and algal-derived or S2 carbon (C) in dated sediment cores from 14 lakes spanning latitudinal and longitudinal gradients across the Canadian high and subarctic. Hg fluxes increased postindustrialization (post-∼1850) in 11 of these lakes (postindustrialization Hg fluxes (ΔHgF(F)) = 2-24 µg m(-2) y(-1)). Correction of HgF(F) for catchment contributions demonstrated that Hg deposition originating from catchment-independent factors, such as atmospheric deposition, increased since industrialization in all 14 lakes. Several of these lakes also showed postindustrial shifts in algal assemblages consistent with climate-induced changes. Eleven lakes showed post-1850s increases in S2F(F), suggesting that lake primary productivity has recently increased in the majority of our sites (ΔS2F(F) = 0.1-4 g m(-2) y(-1)). Other studies have interpreted significant relationships between Hg:S2 concentrations in Arctic sediment as support for the algal scavenging hypothesis, which postulates that Hg fluxes to Arctic sediments are largely driven by S2. However, in six of our lakes we observed no Hg:S2 relationship, and in one lake a significant negative Hg:S2 relationship was observed due to increased Hg and decreased S2 C deposition during the postindustrialization period. In six of the seven lakes where a significant positive Hg:S2 relationship was observed, algal assemblages either did not change through time or the timing of the shifts did not correspond to changes in Hg deposition. Our results demonstrate that, although Arctic lakes are experiencing a myriad of changes, including increased Hg and S2 deposition or changing algal assemblages, increased lake primary productivity does not appear to be driving changes in Hg fluxes to sediments.

Long-term spatial and temporal trends, and source apportionment of polycyclic aromatic compounds in the Athabasca Oil Sands Region.

We investigated the spatio-temporal trends of polycyclic aromatic compounds (PACs) deposition in the Athabasca Oil Sands Region (AOSR) between 2008 and 2017, and applied source apportionment tools to assess sources using snowpacks. Estimated PAC mass deposition was significantly correlated with crude oil production (R2 = 0.48, p = 0.03), and increased between 2008 and 2017. Loadings of alkylated PACs c1-, c2-fluorenes/pyrenes and c1-, c3-benzo[a]anthracenes/chrysenes/triphenylenes significantly increased at mid-field sites (25-50 km from central industrial reference site, AR6) (Mann-Kendall, p < 0.05) reflecting physical expansion of the AOSR. The distance from emission sources was important in the deposition of PACs, including the distance from AR6 (R2 = 0.69-0.91), nearest petcoke storage (R2 = 0.77-0.88), 0.89) and upgrader stack (R2 = 0.56-0.61). Source apportionment PAC distribution profiles of the source materials (petcokes, oil sand ores, road dust) did not show unique matching profiles with the snowpacks. However, the minimal presence of retene in petcokes and an abundance of benzo[ghi]fluoranthene in road dust was observed, and suggests potential for these compounds as chemical markers in distinguishing sources. Furthermore, correlations between PACs and selected metal(loid)s in the AOSR snowpacks were assessed to infer potential common sources. Significant positive (p < 0.05) correlations between metal(loid)s enriched in bitumen (vanadium, molybdenum, nickel) and PACs, at near to mid-field (0-50 km from AR6) sites suggests common sources or similar transfer and fate processes. The results of our study convey data necessary for monitoring studies in the constantly developing AOSR, advance our knowledge of PACs profiles in source materials (including the much less studied alkylated PACs and dibenzothiophenes), which will be valuable for other studies related to oil pollution, urban run-off and forest fires. PACs mass deposition increasing between 2008 and 2017 coincident with crude oil production, and retene and benzo[ghi]fluoranthene show potential in distinguishing AOSR sources.

Atmospheric trace metal deposition to remote Northwest Ontario, Canada: Anthropogenic fluxes and inventories from 1860 to 2010.

National and global inventories of anthropogenic trace element emissions to air is a comparatively recent phenomenon (post-1993 in Canada) as is the monitoring of atmospheric metal deposition, the latter being also very spatially limited. Paleo-reconstructive methods offer a contiguous record of environmental contamination providing a needed framework to establish locally relevant "pre-industrial" (~natural) conditions which can be compare with relative and quantitative deviations away from reference conditions. In this study, we reconstruct the history of the long-range, anthropogenic sourced atmospheric trace element deposition to the remote region of Northwestern Ontario Canada (Experimental Lakes Area (ELA)) using dated sediment records from five lakes. Several elements are shown to be highly enriched in lake sediments relative to pre-1860 sediments (Antimony, Lead, Tellurium, Tin, Arsenic, Bismuth, Cadmium and Mercury) and moderately (Zinc, Tungsten, Thallium, Copper, Silver, Selenium, Nickel and Vanadium). Mean decadal anthropogenic atmospheric fluxes (mg m-2 yr-1) are reconstructed for 1860-2010 and compare well with available local (ELA), regional (NW Ontario Canada, N Michigan USA) monitoring data, as well as global assessments of anthropogenic contribution to atmospheric trace metal burdens. Quantitative paleo reconstructions of atmospheric contamination history using the collective signal from multiple lakes provide a rigorous methodology to assess trends, uncertainties, evaluation with monitoring data and, provide an opportunity to explore landscape processes of contaminant transport and storage. Further study of the latter is recommended to understand the latency of legacy anthropogenic contamination of the environment.

A one-century sedimentary record of N- and S-polycyclic aromatic compounds in the Athabasca oil sands region in Canada.

The atmospheric deposition of polycyclic aromatic compounds (PACs) is considered a major pathway to isolated lakes and bogs in the Athabasca oil sands region (AOSR), Canada. However, the suite of PACs measured has been limited. We report the detailed depositional history of nitrogen and sulphur heterocyclic PACs using a 210Pb dated sediment core (1914-2015) near major developments in the AOSR. We observed (1) an exponential growth in the deposition of heterocyclic PACs to recent times with an average doubling time of 12 years, (2) significant breakpoints in PAC fluxes in the mid to late 1980s, and (3) a synchronous increase of PACs with crude oil production (r2 = 0.82, p = 0.001). NPACs were not detected prior to the 1960s in the sediment core studied, suggesting they may hold promise in serving as indicators for atmospheric PAC deposition of industrial origin. Furthermore, a change in heterocyclic PAC distribution profiles beginning in the 1970-1980s, after the onset of mining, resembling a petcoke signature, was also observed. Significant positive correlations (p < 0.05) were observed between heterocyclic PACs, and several metal(loid)s, including priority pollutant elements, chromium and beryllium, and rare earth elements, cerium, lanthanum and yttrium (r2 > 0.75), suggesting the potential of a common source or similar transport and fate mechanisms. Significant negative or no correlations were observed between heterocyclic PACs and other metal(loid)s, including vanadium, total mercury and lead, possibly reflecting the impact of broader regulatory controls introduced in the mid-1970s on some metal(loids) but not on PACs, including the installation of electrostatic precipitators in major upgrader stacks.