'Paleofloodscapes': Application of sediment source fingerprinting to track flood regime change over space and time at the Peace-Athabasca Delta, Canada.

Deltas are hydrologically dynamic landscapes where river floodwaters create a mosaic of productive ecosystems that provide important services. The flood regime, however, is vulnerable to upstream anthropogenic activities, climate change and geomorphic processes. Deciphering the roles of multiple potential stressors on flood regime change is critical for developing appropriate adaptive and mitigative strategies but requires knowledge of hydrological variability at broader scales of space and time than is typically available from instrumental and observational records. At the globally recognized Peace-Athabasca Delta (Canada), the timing, magnitude and causes of reduced flooding and drawdown of perched basin water levels remain an intense focus of investigation. Here we employ novel 'paleofloodscapes', generated from geospatial interpolation of Bayesian mixing model fingerprinting of sediment elemental concentrations, to quantify variation in the delta's flood regime during the past ~140 years. Results reveal that flooding of the delta began to decline several decades before hydroelectric regulation of Peace River flow, not coincident with it, and the influence of floodwaters from the unregulated Athabasca River has declined more than the regulated Peace River. A key discovery is that widespread flooding of perched basins occurs when ice-jam events on the river(s) coincide with a relatively high water-plane in the delta's open-drainage network. Without knowledge of open-drainage water levels, inferred change to the flood regime of perched basins may be inaccurate when derived solely from analyses of Peace River hydrometric data and climatic records. The paleofloodscapes illustrate that rising sediment delivery caused by a natural river avulsion in 1982 may undermine the intended purpose of a proposed weir installation. The most recent paleofloodscape, developed from lake surface sediment sampling shortly after widespread flooding, demonstrates the value of the approach as a landscape hydrological monitoring tool, and is readily transferrable to other floodplains to track flood regime change.

Paleolimnological evaluation of metal(loid) enrichment from oil sands and gold mining operations in northwestern Canada.

Abundant reserves of metals and oil have spurred large-scale mining developments across northwestern Canada during the past 80 years. Historically, the associated emissions footprint of hazardous metal(loid)s has been difficult to identify, in part, because monitoring records are too short and sparse to have characterized their natural concentrations before mining began. Stratigraphic analysis of lake sediment cores has been employed where concerns of pollution exist to determine pre-disturbance metal(loid) concentrations and quantify the degree of enrichment since mining began. Here, we synthesize the current state of knowledge via systematic re-analysis of temporal variation in sediment metal(loid) concentrations from 51 lakes across four key regions spanning 670 km from bitumen mining in the Alberta Oil Sands Region (AOSR) to gold mining (Giant and Con mines) at Yellowknife in central Northwest Territories. Our compilation includes upland and floodplain lakes at varying distances from the mines to evaluate dispersal of pollution-indicator metal(loid)s from bitumen (vanadium and nickel) and gold mining (arsenic and antimony) via atmospheric and fluvial pathways. Results demonstrate 'severe' enrichment of vanadium and nickel at near-field sites (≤20 km) within the AOSR and 'severe' (near-field; ≤ 40 km) to 'considerable' (far-field; 40-80 km) enrichment of arsenic and antimony due to gold mining at Yellowknife via atmospheric pathways, but no evidence of enrichment of vanadium or nickel via atmospheric or fluvial pathways at the Peace-Athabasca Delta and Slave River Delta. Findings can be used by decision makers to evaluate risks associated with contaminant dispersal by the large-scale mining activities. In addition, we reflect upon methodological approaches to be considered when evaluating paleolimnological data for evidence of anthropogenic contributions to metal(loid) deposition and advocate for proactive inclusion of paleolimnology in the early design stage of environmental contaminant monitoring programs.

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.

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.

Assessment of vanadium and nickel enrichment in Lower Athabasca River floodplain lake sediment within the Athabasca Oil Sands Region (Canada).

Sediment quality monitoring is commonly used to assess for river pollution by industrial activities, but requires knowledge of pre-disturbance conditions. This has long been a critical knowledge gap for assessing pollution of the Lower Athabasca River within the Athabasca Oil Sands Region (AOSR) because sediment quality monitoring started 30 years after mining operations began in 1967. Here, we analyze oil-sands pollution indicator metals vanadium (V) and nickel (Ni) in sediment cores from five Athabasca River floodplain lakes spanning from 17 km upstream to 58 km downstream of central oil sands operations. These data are used to define pre-development baseline (i.e., reference) concentrations and assess for enrichment in sediment deposited after 1967. Measurements of organic and inorganic matter content were used to differentiate periods of strong and weaker Athabasca River influence in the sediment records, as needed to discern pathways of metal deposition. Numerical analyses reveal that post-1967 V and Ni enrichment factors have remained below the 1.5 threshold for 'minimal enrichment' (sensu Birch, 2017) in stratigraphic intervals of strong river influence in the floodplain lakes. Thus, concentrations of V and Ni carried by Athabasca River sediment have not become measurably enriched since onset of oil sands development, as demonstrated by our before-after study design with >99.99% power to detect a 10% increase above pre-development baselines. At the closest lake (<1 km) to oil sands operations, however, enrichment factors for V and Ni increased to 2.1 and 1.5, respectively, in the mid-1980s and have remained at this level when river influence was weaker, indicating contamination via atmospheric transport. Localized enrichment within the oil sands region via atmospheric pathways is a greater concern for ecosystems and society than local and far-field transport by fluvial pathways.

Sources of atmospheric metal(loid) pollution recorded in Thompson Manitoba lake sediment cores within the Canadian boreal biome.

Global atmospheric emissions and subsequent deposition of numerous metal(loid)s has increased markedly since the industrial revolution. Due to a paucity of long-term metal(loid) flux measurements, the magnitude and timing of change are largely unknown, resulting in limited ability to predict time-scales of ecosystem recovery in response to emission decreases. In the absence of long-term data, palaeo-reconstructions provide continuous records of atmospheric metal(loid) deposition on an ecosystem, and landscape, scale. Here, we use high-resolution dated lake sediment cores to reconstruct the last c. 100 years of atmospheric anthropogenic deposition of a full suite (40) of metal(loid)s near a large nickel (Ni) and copper (Cu) smelter in an other-wise largely "pristine" region of northern Canada (Thompson, Manitoba). Anthropogenic depositional fluxes were compared to other regions of Canada including Kejimkujik National Park in Nova Scotia, Experimental Lakes Area in Ontario, as well as the Flin Flon, Manitoba Cu and zinc (Zn) smelter, located ~200 km southwest of Thompson. Deposition of 12 metal(loid)s were enriched above baseline (pre-1915) levels: antimony (Sb) > palladium (Pd) > bismuth (Bi) > mercury (Hg) > cadmium (Cd) > Ni > lead (Pb) > arsenic (As) > strontium (Sr) > Cu > platinum (Pt) > Zn. Spatio-temporal patterns in depositional fluxes and inventories demonstrate that 6 of these metal(loid)s were sourced primarily from the smelter, while As, Hg, Pb, Pt, Sb and Zn were sourced primarily from global and/or regional sources. Comparison of anthropogenic fluxes and inventories to available emissions data showed that Cu and Ni deposition has plateaued since the late 1970s despite dramatic smelter emission decreases between 2005 and 2014. We hypothesize that this discrepancy is due to releases of terrestrial metal(loid)s by climate-driven permafrost degradation, which is widespread across the region and will likely continue to drive increased metal(loid) fluxes to northern Canadian lakes for unknown time-scales.

Use of pre-industrial baselines to monitor anthropogenic enrichment of metals concentrations in recently deposited sediment of floodplain lakes in the Peace-Athabasca Delta (Alberta, Canada).

Well-designed monitoring approaches are needed to assess effects of industrial development on downstream aquatic environments and guide environmental stewardship. Here, we develop and apply a monitoring approach to detect potential enrichment of metals concentrations in surficial lake sediments of the Peace-Athabasca Delta (PAD), northern Alberta, Canada. Since the ecological integrity of the PAD is strongly tied to river floodwaters that replenish lakes in the delta, and the PAD is located downstream of the Alberta oil sands, concerns have been raised over the potential transport of industry-supplied metals to the PAD via the Athabasca River. Surface sediment samples were collected in September 2017 from 61 lakes across the delta, and again in July 2018 from 20 of the same lakes that had received river floodwaters 2 months earlier, to provide snapshots of metals concentrations (Be, Cd, Cr, Cu, Ni, Pb, V, and Zn) that have recently accumulated in these lakes. To assess for anthropogenic enrichment, surficial sediment metals concentrations were normalized to aluminum and compared to pre-industrial baseline (i.e., reference) metal-aluminum linear relations for the Athabasca and Peace sectors of the PAD developed from pre-1920 measurements in lake sediment cores. Numerical analysis demonstrates no marked enrichment of these metals concentrations above pre-1920 baselines despite strong ability (> 99% power) to detect enrichment of 10%. Measurements of river sediment collected by the Regional Aquatics- and Oil Sands-Monitoring Programs (RAMP/OSM) also did not exceed pre-1920 concentrations. Thus, results presented here show no evidence of substantial oil sands-derived metals enrichment of sediment supplied by the Athabasca River to lakes in the PAD and demonstrate the usefulness of these methods as a monitoring framework.

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.

The world's largest High Arctic lake responds rapidly to climate warming.

Using a whole-watershed approach and a combination of historical, contemporary, modeled and paleolimnological datasets, we show that the High Arctic's largest lake by volume (Lake Hazen) has succumbed to climate warming with only a ~1 °C relative increase in summer air temperatures. This warming deepened the soil active layer and triggered large mass losses from the watershed's glaciers, resulting in a ~10 times increase in delivery of glacial meltwaters, sediment, organic carbon and legacy contaminants to Lake Hazen, a >70% decrease in lake water residence time, and near certainty of summer ice-free conditions. Concomitantly, the community assemblage of diatom primary producers in the lake shifted dramatically with declining ice cover, from shoreline benthic to open-water planktonic species, and the physiological condition of the only fish species in the lake, Arctic Char, declined significantly. Collectively, these changes place Lake Hazen in a biogeochemical, limnological and ecological regime unprecedented within the past ~300 years.

Anthropogenic mercury deposition in Flin Flon Manitoba and the Experimental Lakes Area Ontario (Canada): A multi-lake sediment core reconstruction.

High-resolution records of anthropogenic mercury (Hg) deposition were constructed from 9 lakes located 5-75km from the Flin Flon, Manitoba smelter (formerly one of North America's largest atmospheric Hg point sources) and 5 lakes in Experimental Lakes Area (ELA), Ontario; a region remote from major Hg point sources. Anthropogenic Hg deposition, as both a flux and inventory, was determined after accounting for lake-specific natural Hg background concentrations, changes in sedimentation and sediment focusing. Results show that records of anthropogenic flux and inventory of Hg were remarkably consistent among the ELA lakes, but varied by 2 orders of magnitude among Flin Flon lakes. The relation between Hg inventories (normalized for prevailing wind direction) and distance from the smelter was used to estimate the total Hg fallout within a 50km radius in 5year time-steps, thus providing a quantitative spatial-temporal Hg depositional history for the Flin Flon region. The same relation solved for 8 cardinal directions weighted by the inverse of the previously applied wind direction normalization generates a map of Hg inventory and deposition on the landscape (Supplementary video). This novel application of sediment core data constructs a landscape model and allows for a visualization of contaminant deposition with respect to a point major source in both space and time. The propensity for Hg to undergo long-range, even global transport explains why Hg deposition within 50km of Flin Flon was ~11% of estimated releases. That is until smelter releases were reduced >10-fold (post-2000), after which observed deposition exceeded smelter releases, suggesting landscape re-emission/remobilization of legacy Hg is a major ongoing regional source of Hg.

Recent Warming, Rather than Industrial Emissions of Bioavailable Nutrients, Is the Dominant Driver of Lake Primary Production Shifts across the Athabasca Oil Sands Region.

Freshwaters in the Athabasca Oil Sands Region (AOSR) are vulnerable to the atmospheric emissions and land disturbances caused by the local oil sands industry; however, they are also affected by climate change. Recent observations of increases in aquatic primary production near the main development area have prompted questions about the principal drivers of these limnological changes. Is the enhanced primary production due to deposition of nutrients (nitrogen and phosphorus) from local industry or from recent climatic changes? Here, we use downcore, spectrally-inferred chlorophyll-a (VRS-chla) profiles (including diagenetic products) from 23 limnologically-diverse lakes with undisturbed catchments to characterize the pattern of primary production increases in the AOSR. Our aim is to better understand the relative roles of the local oil sands industry versus climate change in driving aquatic primary production trends. Nutrient deposition maps, generated using geostatistical interpolations of spring-time snowpack measurements from a grid pattern across the AOSR, demonstrate patterns of elevated total phosphorus, total nitrogen, and bioavailable nitrogen deposition around the main area of industrial activity. However, this pattern is not observed for bioavailable phosphorus. Our paleolimnological findings demonstrate consistently greater VRS-chla concentrations compared to pre-oil sands development levels, regardless of morphological and limnological characteristics, landscape position, bioavailable nutrient deposition, and dibenzothiophene (DBT)-inferred industrial impacts. Furthermore, breakpoint analyses on VRS-chla concentrations across a gradient of DBT-inferred industrial impact show limited evidence of a contemporaneous change among lakes. Despite the contribution of bioavailable nitrogen to the landscape from industrial activities, we find no consistency in the spatial pattern and timing of VRS-chla shifts with an industrial fertilizing signal. Instead, significant positive correlations were observed between VRS-chla and annual and seasonal temperatures. Our findings suggest warmer air temperatures and likely decreased ice covers are important drivers of enhanced aquatic primary production across the AOSR.

Characterizing baseline concentrations, proportions, and processes controlling deposition of river-transported bitumen-associated polycyclic aromatic compounds at a floodplain lake (Slave River Delta, Northwest Territories, Canada).

Inadequate knowledge of baseline conditions challenges ability for monitoring programs to detect pollution in rivers, especially where there are natural sources of contaminants. Here, we use paleolimnological data from a flood-prone lake ("SD2", informal name) in the Slave River Delta (SRD, Canada), ∼ 500 km downstream of the Alberta oil sands development and the bitumen-rich McMurray Formation to identify baseline concentrations and proportions of "river-transported bitumen-associated indicator polycyclic aromatic compounds" (indicator PACs; Hall et al. 2012) and processes responsible for their deposition. Results show that indicator PACs are deposited in SD2 by Slave River floodwaters in concentrations that are 45 % lower than those in sediments of "PAD31compounds", a lake upstream in the Athabasca Delta that receives Athabasca River floodwaters. Lower concentrations at SD2 are likely a consequence of sediment retention upstream as well as dilution by sediment influx from the Peace River. In addition, relations with organic matter content reveal that flood events dilute concentrations of indicator PACs in SD2 because the lake receives high-energy floods and the lake sediments are predominantly inorganic. This contrasts with PAD31 where floodwaters increase indicator PAC concentrations in the lake sediments, and concentrations are diluted during low flood influence intervals due to increased deposition of lacustrine organic matter. Results also show no significant differences in concentrations and proportions of indicator PACs between pre- (1967) and post- (1980s and 1990 s) oil sands development high flood influence intervals (t = 1.188, P = 0.279, d.f. = 6.136), signifying that they are delivered to the SRD by natural processes. Although we cannot assess potential changes in indicator PACs during the past decade, baseline concentrations and proportions can be used to enhance ongoing monitoring efforts.

Spatiotemporal patterns of mercury accumulation in lake sediments of western North America.

For the Western North America Mercury Synthesis, we compiled mercury records from 165 dated sediment cores from 138 natural lakes across western North America. Lake sediments are accepted as faithful recorders of historical mercury accumulation rates, and regional and sub-regional temporal and spatial trends were analyzed with descriptive and inferential statistics. Mercury accumulation rates in sediments have increased, on average, four times (4×) from 1850 to 2000 and continue to increase by approximately 0.2µg/m(2) per year. Lakes with the greatest increases were influenced by the Flin Flon smelter, followed by lakes directly affected by mining and wastewater discharges. Of lakes not directly affected by point sources, there is a clear separation in mercury accumulation rates between lakes with no/little watershed development and lakes with extensive watershed development for agricultural and/or residential purposes. Lakes in the latter group exhibited a sharp increase in mercury accumulation rates with human settlement, stabilizing after 1950 at five times (5×) 1850 rates. Mercury accumulation rates in lakes with no/little watershed development were controlled primarily by relative watershed size prior to 1850, and since have exhibited modest increases (in absolute terms and compared to that described above) associated with (regional and global) industrialization. A sub-regional analysis highlighted that in the ecoregion Northwestern Forest Mountains, <1% of mercury deposited to watersheds is delivered to lakes. Research is warranted to understand whether mountainous watersheds act as permanent sinks for mercury or if export of "legacy" mercury (deposited in years past) will delay recovery when/if emissions reductions are achieved.

Paleolimnological assessment of riverine and atmospheric pathways and sources of metal deposition at a floodplain lake (Slave River Delta, Northwest Territories, Canada).

Growth of natural resource development in northern Canada has raised concerns about the effects on downstream aquatic ecosystems, but insufficient knowledge of pre-industrial baseline conditions continues to undermine ability of monitoring programs to distinguish industrial-derived contaminants from those supplied by natural processes. Here, we apply a novel paleolimnological approach to define pre-industrial baseline concentrations of 13 priority pollutant metals and vanadium and assess temporal changes, pathways and sources of these metals at a flood-prone lake (SD2) in the Slave River Delta (NWT, Canada) located ~500 km north of Alberta's oil sands development and ~140 km south of a former gold mine at Yellowknife, NWT. Results identify that metal concentrations, normalized to lithium concentration, are not elevated in sediments deposited during intervals of high flood influence or low flood influence since onset of oil sands development (post-1967) relative to the 1920-1967 baseline established at SD2. When compared to a previously defined baseline for the upstream Athabasca River, several metal-Li relations (Cd, Cr, Ni, Zn, V) in post-1967 sediments delivered by floodwaters appear to plot along a different trajectory, suggesting that the Peace and Slave River watersheds are important natural sources of metal deposition at the Slave River Delta. However, analysis revealed unusually high concentrations of As deposited during the 1950s, an interval of very low flood influence at SD2, which corresponded closely with emission history of the Giant Mine gold smelter indicating a legacy of far-field atmospheric pollution. Our study demonstrates the potential for paleolimnological characterization of baseline conditions and detection of pollution from multiple pathways in floodplain ecosystems, but that knowledge of paleohydrological conditions is essential for interpretation of contaminant profiles.

Source Apportionment of Background PAHs in the Peace-Athabasca Delta (Alberta, Canada) Using Molecular Level Radiocarbon Analysis.

The downstream accumulation of polycyclic aromatic hydrocarbons (PAHs) in the Peace-Athabasca Delta (PAD), an ecologically important landscape, is a key issue of concern given the rapid development of the oil sands industry in Northern Alberta, Canada. In addition to PAHs derived from industrial activity (i.e., oil sands mining) within the Athabasca watershed, however, forest fires and erosion of fossil fuel deposits within both the Athabasca and Peace watersheds are two potentially important natural sources of PAHs delivered to the PAD. Consequently, evaluating the environmental impact of mining activities requires a quantitative understanding of natural, background PAHs. Here, we utilize molecular-level natural-abundance radiocarbon measurements on an amalgamated sediment record from a Peace River flood-susceptible oxbow lake in the northern Peace sector of the PAD to quantitatively discriminate sources of naturally occurring alkylated PAHs (fossil and modern biomass). A radiocarbon mass balance quantified a predominantly natural petrogenic source (93% petrogenic, 7% forest fire) for alkylated PAHs during the past ∼50 years. Additionally, a significant petrogenic component determined for retene, a compound usually considered a biomarker for softwood combustion, suggests that its use as a unique forest fire indicator may not be suitable in PAD sediments receiving Peace watershed-derived fluvial inputs.

Has Alberta oil sands development altered delivery of polycyclic aromatic compounds to the Peace-Athabasca Delta?

BACKGROUND: The extent to which Alberta oil sands mining and upgrading operations have enhanced delivery of bitumen-derived contaminants via the Athabasca River and atmosphere to the Peace-Athabasca Delta (200 km to the north) is a pivotal question that has generated national and international concern. Accounts of rare health disorders in residents of Fort Chipewyan and deformed fish in downstream ecosystems provided impetus for several recent expert-panel assessments regarding the societal and environmental consequences of this multi-billion-dollar industry. Deciphering relative contributions of natural versus industrial processes on downstream supply of polycyclic aromatic compounds (PACs) has been identified as a critical knowledge gap. But, this remains a formidable scientific challenge because loading from natural processes remains unknown. And, industrial activity occurs in the same locations as the natural bitumen deposits, which potentially confounds contemporary upstream-downstream comparisons of contaminant levels. METHODS/PRINCIPAL FINDINGS: Based on analyses of lake sediment cores, we provide evidence that the Athabasca Delta has been a natural repository of PACs carried by the Athabasca River for at least the past two centuries. We detect no measureable increase in the concentration and proportion of river-transported bitumen-associated indicator PACs in sediments deposited in a flood-prone lake since onset of oil sands development. Results also reveal no evidence that industrial activity has contributed measurably to sedimentary concentration of PACs supplied by atmospheric transport. CONCLUSIONS/SIGNIFICANCE: Findings suggest that natural erosion of exposed bitumen in banks of the Athabasca River and its tributaries is a major process delivering PACs to the Athabasca Delta, and the spring freshet is a key period for contaminant mobilization and transport. This baseline environmental information is essential for informed management of natural resources and human-health concerns by provincial and federal regulatory agencies and industry, and for designing effective long-term monitoring programs for the lower Athabasca River watershed.

Has Alberta oil sands development increased far-field delivery of airborne contaminants to the Peace-Athabasca Delta?

Identifying potential regional contamination by Alberta oil sands industrial emissions on sensitive ecosystems like the Peace-Athabasca Delta, ~200 km to the north, requires knowledge of historical contaminant levels and trends. Here we provide some of these critically-needed data, based on analysis of metals in a sediment core from an upland precipitation-fed lake in the delta. The lake is well-situated to record the anthropogenic history of airborne contaminant deposition for this region. Sediment records of metals of concern (Pb, Sb, As, Hg) reflect early to mid-20th century increases in North American industrial emissions, followed by reduced emissions due to improved industrial practices after 1950-70. Notably, Pb, Sb, As and Hg have declined since the onset of Alberta oil sands production, belying concerns that this activity has enhanced far-field atmospheric delivery of these contaminants to the delta.