Tracking petrogenic hydrocarbons in lakes of the Peace-Athabasca Delta in Alberta, Canada using petroleum biomarkers.

The Peace-Athabasca Delta (PAD) receives a mixture of hydrocarbons from biogenic, pyrogenic, and petrogenic processes. Source apportionment in the PAD has focussed on polycyclic aromatic compounds (PACs), which are ubiquitous in the environment and susceptible to weathering. In contrast, petroleum biomarkers of terpanes, hopanes, and steranes are degradation-resistant organic compounds found uniquely in petroleum products that can identify the input and origin of petrogenic hydrocarbons (PHCs). We provide an analysis of environmentally-relevant PHCs (including n-alkanes, PACs, and petroleum biomarkers) in surficial sediments of strategically selected lakes in the Athabasca and Peace deltas and adjacent boreal uplands. Alkanes were found to be predominately biogenic in all lakes. PAC sources were identified as wood combustion in the upland boreal lakes, a mixture of petrogenic and pyrogenic combustion in two closed-drainage lakes in the Peace Delta, and predominately petrogenic in two flood-prone Athabasca Delta lakes. Using multivariate analyses, raw Alberta oil sands were identified as a potential source of PHCs to the two flood-prone lakes in the Athabasca Delta. Biomarkers of terpanes and hopanes were identified in the Peace Delta and boreal uplands, likely from bitumen and transported atmospherically. These findings validate the use of petroleum biomarkers as tracers for bituminous sands in surficial lake sediments and their potential use in paleolimnological investigations at the PAD to improve understanding of relative roles of natural and industrial processes on far-field deposition of PHCs.

Determining the effects of past gold mining using a sediment palaeotoxicity model.

Ore processing techniques used in Yellowknife's largest mining operation, Giant Mine, is responsible for the atmospheric release of approximately 20,000 t of particulate arsenic trioxide and other heavy metal(loids). This rapid deposition of heavy metal(loids) may have caused ecological disturbances to aquatic food webs. Here we use 210Pb and 137Cs dated lake sediment cores from 20 lakes within a 40 km radius of Yellowknife to examine the spatial-temporal distribution of arsenic, antimony and lead. Further, we model the toxicity of the sediment to aquatic biota pre-, during, and post-mining using palaeotoxicity modelling, enrichment factor assessment, and comparisons to national sediment quality guidelines. We found that metal(loid) profiles in sediment peaked during the height of mining operations. These peak metal(loid) concentrations were highest in lakes near the mine's roaster stack, and decreased with distance from the historic mine. Palaeotoxicity modelling of lake sediment archives indicate that there is no significant difference in the mean predicted toxicity of pre- and post-mining samples (p = 0.14), however mining activities in the region significantly increased the predicted toxicity of sediments to aquatic organisms during mining operations (p < 0.001). In the years since roasting processes ceased, the mean palaeotoxicity of all lakes has decreased significantly (p < 0.05), indicating a projected pattern of biological recovery. Importantly, some lakes remain at an elevated risk, indicating that aquatic ecosystems in Yellowknife may continue to have lingering effects on aquatic biota despite the closure of the mine two decades ago.

Comparative histories of polycyclic aromatic compound accumulation in lake sediments near petroleum operations in western Canada.

We examined the historical deposition of polycyclic aromatic compounds (PACs) recorded in radiometrically-dated lake sediment cores from a small, conventional oil and gas operation in the southern Northwest Territories (Cameron Hills), and placed these results in the context of previously published work from three other important regions of western Canada: (1) the Athabasca oil sands region in Alberta; (2) Cold Lake, Alberta; and (3) the Mackenzie Delta, NT. Sediment PAC records from the Cameron Hills showed no clear changes in either source or concentrations coincident with the timing of development in these regions. Changes were small in comparison to the clear increases in both parent and alkyl-substituted PACs in response to industrial development from the Athabasca region surface mining of oil sands, where parent PAC diagnostic ratios indicated a shift from pyrogenic sources (primarily wood and coal burning) in pre-development sediments to more petrogenically-sourced PACs in modern sediments. Cores near in-situ oil sand extraction operations showed only modest increases in PAC deposition. This work directly compares the history and trajectory of contamination in lake ecosystems in areas of western Canada impacted by the most common types of hydrocarbon extraction activities, and provides a context for assessing the environmental impacts of oil and gas development in the future.

Paleo-ecotoxicology: What Can Lake Sediments Tell Us about Ecosystem Responses to Environmental Pollutants?

The development of effective risk reduction strategies for aquatic pollutants requires a comprehensive understanding of toxic impacts on ecosystems. Classical toxicological studies are effective for characterizing pollutant impacts on biota in a controlled, simplified environment. Nonetheless, it is well-acknowledged that predictions based on the results of these studies must be tested over the long-term in a natural ecosystem setting to account for increased complexity and multiple stressors. Paleolimnology (the study of lake sediment cores to reconstruct environmental change) can address many key knowledge gaps. When used as part of a weight-of-evidence framework with more traditional approaches in ecotoxicology, it can facilitate rapid advances in our understanding of the chronic effects of pollutants on ecosystems in an environmentally realistic, multistressor context. Paleolimnology played a central role in the Acid Rain debates, as it was instrumental in demonstrating industrial emissions caused acidification of lakes and associated ecosystem-wide impacts. "Resurrection Ecology" (hatching dormant resting eggs deposited in the past) records evolutionary responses of populations to chronic pollutant exposure. With recent technological advances (e.g., geochemistry, genomic approaches), combined with an emerging paleo-ecotoxicological framework that leverages strengths across multiple disciplines, paleolimnology will continue to provide valuable insights into the most pressing questions in ecotoxicology.

Broad-scale lake expansion and flooding inundates essential wood bison habitat.

Understanding the interaction between the response of a complex ecosystem to climate change and the protection of vulnerable wildlife species is essential for conservation efforts. In the Northwest Territories (Canada), the recent movement of the Mackenzie wood bison herd (Bison bison athabascae) out of their designated territory has been postulated as a response to the loss of essential habitat following regional lake expansion. We show that the proportion of this landscape occupied by water doubled since 1986 and the timing of lake expansion corresponds to bison movements out of the Mackenzie Bison Sanctuary. Historical reconstructions using proxy data in dated sediment cores show that the scale of recent lake expansion is unmatched over at least the last several hundred years. We conclude that recent lake expansion represents a fundamental alteration of the structure and function of this ecosystem and its use by Mackenzie wood bison, in response to climate change.

Multi-trophic level response to extreme metal contamination from gold mining in a subarctic lake.

Giant Mine, located in the city of Yellowknife (Northwest Territories, Canada), is a dramatic example of subarctic legacy contamination from mining activities, with remediation costs projected to exceed $1 billion. Operational between 1948 and 2004, gold extraction at Giant Mine released large quantities of arsenic and metals from the roasting of arsenopyrite ore. We examined the long-term ecological effects of roaster emissions on Pocket Lake, a small lake at the edge of the Giant Mine lease boundary, using a spectrum of palaeoenvironmental approaches. A dated sedimentary profile tracked striking increases (approx. 1700%) in arsenic concentrations coeval with the initiation of Giant Mine operations. Large increases in mercury, antimony and lead also occurred. Synchronous changes in biological indicator assemblages from multiple aquatic trophic levels, in both benthic and pelagic habitats, indicate dramatic ecological responses to extreme metal(loid) contamination. At the peak of contamination, all Cladocera, a keystone group of primary consumers, as well as all planktonic diatoms, were functionally lost from the sediment record. No biological recovery has been inferred, despite the fact that the bulk of metal(loid) emissions occurred more than 50 years ago, and the cessation of all ore-roasting activities in Yellowknife in 1999.

Assessing the contribution of combustion-derived contaminants to a remote subarctic environment from traffic on the Tibbitt to Contwoyto winter road (Northwest Territories, Canada).

Remote mining operations in Canada's Northwest Territories and Nunavut are supported by a 600 km winter road, which spans the transition from subarctic boreal forest in Yellowknife to low Arctic tundra. Each year, thousands of truckloads of fuel, large equipment, and other heavy loads are hauled up the winter road. We investigated whether diesel emissions from commercial truck traffic is a major source of metals and polycyclic aromatic compounds (PACs) to aquatic ecosystems along the winter road. In March 2014, at the end of the hauling season, we collected integrated snow samples, water, and sediment from nine lakes located along the winter road, as well as from six lakes located within the city of Yellowknife. Examination of PAC composition and diagnostic ratios in snow samples showed that wildfires are an important source of PACs to lakes along the winter road, while anthropogenic sources are more prevalent in snow from Yellowknife lakes. Concentrations of PACs, including those associated with diesel emissions, were variable in snow, water, and sediment across all sites. The highest concentrations of PACs in snow were reported in winter road lakes located in the subarctic boreal forest, where forest fires are common. No compositional differences were observed for PACs in sediment and water samples between Yellowknife and winter road lakes. We did not observe any evidence of metal contamination in snow collected along the winter road, and metal concentrations in snow from winter road sites were consistently lower than Yellowknife sites. Our results show that a high contribution of PACs from natural sources can obscure potential contributions from diesel traffic emissions along the winter road.

Exploratory hydrocarbon drilling impacts to Arctic lake ecosystems.

Recent attention regarding the impacts of oil and gas development and exploitation has focused on the unintentional release of hydrocarbons into the environment, whilst the potential negative effects of other possible avenues of environmental contamination are less well documented. In the hydrocarbon-rich and ecologically sensitive Mackenzie Delta region (NT, Canada), saline wastes associated with hydrocarbon exploration have typically been disposed of in drilling sumps (i.e., large pits excavated into the permafrost) that were believed to be a permanent containment solution. However, failure of permafrost as a waste containment medium may cause impacts to lakes in this sensitive environment. Here, we examine the effects of degrading drilling sumps on water quality by combining paleolimnological approaches with the analysis of an extensive present-day water chemistry dataset. This dataset includes lakes believed to have been impacted by saline drilling fluids leaching from drilling sumps, lakes with no visible disturbances, and lakes impacted by significant, naturally occurring permafrost thaw in the form of retrogressive thaw slumps. We show that lakes impacted by compromised drilling sumps have significantly elevated lakewater conductivity levels compared to control sites. Chloride levels are particularly elevated in sump-impacted lakes relative to all other lakes included in the survey. Paleolimnological analyses showed that invertebrate assemblages appear to have responded to the leaching of drilling wastes by a discernible increase in a taxon known to be tolerant of elevated conductivity coincident with the timing of sump construction. This suggests construction and abandonment techniques at, or soon after, sump establishment may result in impacts to downstream aquatic ecosystems. With hydrocarbon development in the north predicted to expand in the coming decades, the use of sumps must be examined in light of the threat of accelerated permafrost thaw, and the potential for these industrial wastes to impact sensitive Arctic ecosystems.

Spatial and temporal assessment of mercury and organic matter in thermokarst affected lakes of the Mackenzie Delta uplands, NT, Canada.

We examined dated sediment cores from 14 thermokarst affected lakes in the Mackenzie Delta uplands, NT, Arctic Canada, using a case-control analysis to determine how retrogressive thaw slump development from degrading permafrost affected the delivery of mercury (Hg) and organic carbon (OC) to lakes. We show that sediments from the lakes with retrogressive thaw slump development on their shorelines (slump-affected lakes) had higher sedimentation rates and lower total Hg (THg), methyl mercury (MeHg), and lower organic carbon concentrations compared to lakes where thaw slumps were absent (reference lakes). There was no difference in focus-corrected Hg flux to sediments between reference lakes and slump-affected lakes, indicating that the lower sediment Hg concentration in slump-affected lakes was due to dilution by rapid inorganic sedimentation in the slump-affected lakes. Sedimentation rates were inversely correlated with THg concentrations in sediments among the 14 lakes considered, and explained 68% of the variance in THg concentration in surface sediment, further supporting the dilution hypothesis. We observed higher S2 (algal-derived carbon) and particulate organic carbon (POC) concentrations in sediment profiles from reference lakes than in slump lakes, likely because of dilution by inorganic siliciclastic matter in cores from slump-affected lakes. We conclude that retrogressive thaw slump development increases inorganic sedimentation in lakes, and decreases concentrations of organic carbon and associated Hg and MeHg in sediments.

Anomalous rise in algal production linked to lakewater calcium decline through food web interactions.

Increased algal blooms are a threat to aquatic ecosystems worldwide, although the combined effects of multiple stressors make it difficult to determine the underlying causes. We explore whether changes in trophic interactions in response to declining calcium (Ca) concentrations, a water quality issue only recently recognized in Europe and North America, can be linked with unexplained bloom production. Using a palaeolimnological approach analysing the remains of Cladocera (herbivorous grazers) and visual reflectance spectroscopically inferred chlorophyll a from the sediments of a Nova Scotia (Canada) lake, we show that a keystone grazer, Daphnia, declined in the early 1990s and was replaced by a less effective grazer, Bosmina, while inferred chlorophyll a levels tripled at constant total phosphorus (TP) concentrations. The decline in Daphnia cannot be attributed to changes in pH, thermal stratification or predation, but instead is linked to declining lakewater [Ca]. The consistency in the timing of changes in Daphnia and inferred chlorophyll a suggests top-down control on algal production, providing, to our knowledge, the first evidence of a link between lakewater [Ca] decline and elevated algal production mediated through the effects of [Ca] decline on Daphnia. [Ca] decline has severe implications for whole-lake food webs, and presents yet another mechanism for potential increases in algal blooms.

Impacts of a recent storm surge on an Arctic delta ecosystem examined in the context of the last millennium.

One of the most ominous predictions related to recent climatic warming is that low-lying coastal environments will be inundated by higher sea levels. The threat is especially acute in polar regions because reductions in extent and duration of sea ice cover increase the risk of storm surge occurrence. The Mackenzie Delta of northwest Canada is an ecologically significant ecosystem adapted to freshwater flooding during spring breakup. Marine storm surges during the open-water season, which move saltwater into the delta, can have major impacts on terrestrial and aquatic systems. We examined growth rings of alder shrubs (Alnus viridis subsp. fruticosa) and diatoms preserved in dated lake sediment cores to show that a recent marine storm surge in 1999 caused widespread ecological changes across a broad extent of the outer Mackenzie Delta. For example, diatom assemblages record a striking shift from freshwater to brackish species following the inundation event. What is of particular significance is that the magnitude of this recent ecological impact is unmatched over the > 1,000-year history of this lake ecosystem. We infer that no biological recovery has occurred in this lake, while large areas of terrestrial vegetation remain dramatically altered over a decade later, suggesting that these systems may be on a new ecological trajectory. As climate continues to warm and sea ice declines, similar changes will likely be repeated in other coastal areas of the circumpolar Arctic. Given the magnitude of ecological changes recorded in this study, such impacts may prove to be long lasting or possibly irreversible.

Trophic position influences the efficacy of seabirds as metal biovectors.

Seabirds represent a well documented biological transport pathway of nutrients from the ocean to the land by nesting in colonies and providing organic subsidies (feces, carcasses, dropped food) to these sites. We investigated whether seabirds that feed at different trophic levels vary in their potency as biovectors of metals, which can bioaccumulate through the marine foodweb. Our study site, located on a small island in Arctic Canada, contains the unique scenario of two nearby ponds, one of which receives inputs almost exclusively from upper trophic level piscivores (Arctic terns, Sterna paradisaea) and the other mainly from lower trophic level molluscivores (common eiders, Somateria mollissima). We used dated sediment cores to compare differences in diatoms, metal concentrations and also stable isotopes of nitrogen (delta(15)N), which reflect trophic position. We show that the seabirds carry species-specific mixtures of metals that are ultimately shunted to their nesting sites. For example, sediments from the tern-affected pond recorded the highest levels of delta(15)N and the greatest concentrations of metals that are known to bioaccumulate, including Hg and Cd. In contrast, the core from the eider-affected site registered lower delta(15)N values, but higher concentrations of Pb, Al, and Mn. These metals have been recorded at their greatest concentrations in eiders relative to other seabirds, including Arctic terns. These data indicate that metals may be used to track seabird population dynamics, and that some metal tracers may even be species-specific. The predominance of large seabird colonies on every continent suggests that similar processes are operating along coastlines worldwide.