Pharmaceutical pollution of the world's rivers.

Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world's rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.

A 2200-year record of Andean Condor diet and nest site usage reflects natural and anthropogenic stressors.

Understanding how animals respond to large-scale environmental changes is difficult to achieve because monitoring data are rarely available for more than the past few decades, if at all. Here, we demonstrate how a variety of palaeoecological proxies (e.g. isotopes, geochemistry and DNA) from an Andean Condor (Vultur gryphus) guano deposit from Argentina can be used to explore breeding site fidelity and the impacts of environmental changes on avian behaviour. We found that condors used the nesting site since at least approximately 2200 years ago, with an approximately 1000-year nesting frequency slowdown from ca 1650 to 650 years before the present (yr BP). We provide evidence that the nesting slowdown coincided with a period of increased volcanic activity in the nearby Southern Volcanic Zone, which resulted in decreased availability of carrion and deterred scavenging birds. After returning to the nest site ca 650 yr BP, condor diet shifted from the carrion of native species and beached marine animals to the carrion of livestock (e.g. sheep and cattle) and exotic herbivores (e.g. red deer and European hare) introduced by European settlers. Currently, Andean Condors have elevated lead concentrations in their guano compared to the past, which is associated with human persecution linked to the shift in diet.

Chemical Weathering Patterns of Diluted Bitumen Spilled into Freshwater Limnocorrals.

Due to the sudden nature of oil spills, few controlled studies have documented how oil weathers immediately following accidental release into a natural lake environment. Here, we evaluated the weathering patterns of Cold Lake Winter Blend, a diluted bitumen (dilbit) product, by performing a series of controlled spills into limnocorrals installed in a freshwater lake in Northern Ontario, Canada. Using a regression-based design, we added seven different dilbit volumes, ranging from 1.5 to 180 L, resulting in oil-to-water ratios between 1:71,000 (v/v) and 1:500 (v/v). We monitored changes in the composition of various petroleum hydrocarbons (PHCs), including n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and oil biomarkers in dilbit over time, as it naturally weathered for 70 days. Depletion rate constants (kD) of n-alkanes and PAHs ranged from 0.0009 to 0.41 d-1 and 0.0008 to 0.38 d-1, respectively. There was no significant relationship between kD and spill volume, suggesting that spill size did not influence the depletion of petroleum hydrocarbons from the slick. Diagnostic ratios calculated from concentrations of n-alkanes, isoprenoids, and PAHs indicated that evaporation and photooxidation were major processes contributing to dilbit weathering, whereas dissolution and biodegradation were less important. These results demonstrate the usefulness of large scale field studies carried out under realistic environmental conditions to elucidate the role of different weathering processes following a dilbit spill.

Use of silicone wristbands to measure firefighters' exposures to polycyclic aromatic hydrocarbons (PAHs) during live fire training.

Firefighters experience exposures to carcinogenic and mutagenic substances, including polycyclic aromatic hydrocarbons (PAHs). Silicone wristbands (SWBs) have been used as passive samplers to assess firefighters' exposures over the course of a shift but their utility in measuring short term exposures, source of exposure, and correlations with other measurements of exposure have not yet been investigated. In this study, SWBs were used to measure the concentrations of 16 priority PAHs inside and outside of firefighters' personal protective equipment (PPE) while firefighting. SWBs were placed on the wrist and jacket of 20 firefighters conducting live fire training. Correlations were made with matching data from a sister project that measured urinary concentrations of PAH metabolites and PAH concentrations from personal air samples from the same participants. Naphthalene, acenaphthylene and phenanthrene had the highest geometric mean concentrations in both jacket and wrist SWB, with 1040, 320, 180 ng/g SWB for jacket and 55.0, 4.9, and 6.0 ng/g SWB for wrist, respectively. Ratios of concentrations between the jacket and wrist SWBs were calculated as worker protection factors (WPFs) and averaged 40.1 for total PAHs and ranged from 2.8 to 214 for individual PAHs, similar to previous studies. Several significant correlations were observed between PAHs in jacket SWBs and air samples (e.g., total and low molecular weight PAHs, r = 0.55 and 0.59, p < 0.05, respectively). A few correlations were found between PAHs from SWBs worn on the wrist and jacket, and urinary concentrations of PAH metabolites and PAH concentrations in air samples. The ability of the SWBs to accurately capture exposures to various PAHs was likely influenced by short sampling time, high temperatures, and high turbulence. Future work should further examine the limitations of SWBs for PAH exposures in firefighting, and other extreme environments.

Linking 19th century European settlement to the disruption of a seabird's natural population dynamics.

Recent estimates indicate that ∼70% of the world's seabird populations have declined since the 1950s due to human activities. However, for almost all bird populations, there is insufficient long-term monitoring to understand baseline (i.e., preindustrial) conditions, which are required to distinguish natural versus anthropogenically driven changes. Here, we address this lack of long-term monitoring data with multiproxy paleolimnological approaches to examine the long-term population dynamics of a major colony of Leach's Storm-petrel (Hydrobates leucorhous) on Grand Colombier Island in the St. Pierre and Miquelon archipelago-an overseas French territory in the northwest Atlantic Ocean. By reconstructing the last ∼5,800 y of storm-petrel dynamics, we demonstrate that this colony underwent substantial natural fluctuations until the start of the 19th century, when population cycles were disrupted, coinciding with the establishment and expansion of a European settlement. Our paleoenvironmental data, coupled with on-the-ground population surveys, indicate that the current colony is only ∼16% of the potential carrying capacity, reinforcing concerning trends of globally declining seabird populations. As seabirds are sentinel species of marine ecosystem health, such declines provide a call to action for global conservation. In response, we emphasize the need for enlarged protected areas and the rehabilitation of disturbed islands to protect ecologically critical seabird populations. Furthermore, long-term data, such as those provided by paleoecological approaches, are required to better understand shifting baselines in conservation to truly recognize current rates of ecological loss.

Effectiveness of dermal cleaning interventions for reducing firefighters' exposures to PAHs and genotoxins.

Firefighters are exposed to carcinogenic and mutagenic combustion emissions, including polycyclic aromatic hydrocarbons (PAHs). Fire service and firefighter cancer advocacy groups recommend skin cleaning using wipes or washing with detergent and water after exposure to smoke, although these strategies have not been proven to reduce exposures to harmful combustion products such as PAHs. This study assessed dermal decontamination methods to reduce PAH exposures by firefighters participating in live fire training scenarios. Study participants (n = 88) were randomly assigned to an intervention group (i.e., two types of commercial skin wipes, detergent and water, or a control group who did not use any skin decontamination). PAHs were measured in personal air (during the fire) and dermal wipe samples (before and after fire suppression and after dermal decontamination). PAH metabolites and mutagenicity were measured in urine samples before and after fire suppression. Airborne PAH concentrations during the fire ranged between 200 and 3,970 µg/m3 (mean = 759 µg/m3, SD = 685 µg/m3). Firefighters had higher total PAHs and high-molecular-weight PAHs on their skin after the fire compared to before (1.3- and 2.2-fold, respectively, p < 0.01). Urinary PAH metabolites increased significantly following exposure to the training fires by 1.7 to 2.2-fold (depending on the metabolite, p < 0.001). Urinary mutagenicity did not differ significantly between pre- and post-fire for any of the decontamination methods. Detergent and water was the only intervention that removed a significant amount of total PAHs from the skin (0.72 ng/cm2 preintervention vs. 0.38 ng/cm2 postintervention, p < 0.01). However, fold changes in urinary PAH metabolites (i.e., pre- vs. post-exposure levels) did not differ among any of the dermal decontamination methods or the control group. These data suggest that despite on-site attempts to remove PAHs from firefighters' skin, the examined interventions did not reduce the internal dose of PAHs. Future work should investigate preventing initial exposure using other interventions, such as improved personal protective equipment.

Climate oscillations drive millennial-scale changes in seabird colony size.

Seabird population size is intimately linked to the physical, chemical, and biological processes of the oceans. Yet, the overall effects of long-term changes in ocean dynamics on seabird colonies are difficult to quantify. Here, we used dated lake sediments to reconstruct ~10,000-years of seabird dynamics in the Northwest Atlantic to determine the influences of Holocene-scale climatic oscillations on colony size. On Baccalieu Island (Newfoundland and Labrador, Canada)-where the world's largest colony of Leach's storm-petrel (Hydrobates leucorhous Vieillot 1818) currently breeds-our data track seabird colony growth in response to warming during the Holocene Thermal Maximum (ca. 9000 to 6000 BP). From ca. 5200 BP to the onset of the Little Ice Age (ca. 550 BP), changes in colony size were correlated to variations in the North Atlantic Oscillation (NAO). By contrasting the seabird trends from Baccalieu Island to millennial-scale changes of storm-petrel populations from Grand Colombier Island (an island in the Northwest Atlantic that is subjected a to different ocean climate), we infer that changes in NAO influenced the ocean circulation, which translated into, among many things, changes in pycnocline depth across the Northwest Atlantic basin where the storm-petrels feed. We hypothesize that the depth of the pycnocline is likely a strong bottom-up control on surface-feeding storm-petrels through its influence on prey accessibility. Since the Little Ice Age (LIA), the effects of ocean dynamics on seabird colony size have been altered by anthropogenic impacts. Subsequently, the colony on Baccalieu Island grew at an unprecedented rate to become the world's largest resulting from favorable conditions linked to climate warming, increased vegetation (thereby nesting habitat), and attraction of recruits from other colonies that are now in decline. We show that although ocean dynamics were an important driver of seabird colony dynamics, its recent influence has been modified by human interference.

Multicentury perspective assessing the sustainability of the historical harvest of seaducks.

Where available, census data on seabirds often do not extend beyond a few years or decades, challenging our ability to identify drivers of population change and to develop conservation policies. Here, we reconstruct long-term population dynamics of northern common eiders (Somateria mollissima borealis). We analyzed sterols together with stable nitrogen isotopes in dated pond sediment cores to show that eiders underwent broadscale population declines over the 20th century at Canadian subarctic breeding sites. Likely, a rapidly growing Greenland population, combined with relocation of Inuit to larger Arctic communities and associated increases in the availability of firearms and motors during the early to mid-20th century, generated more efficient hunting practices, which in turn reduced the number of adult eiders breeding at Canadian nesting islands. Our paleolimnological approach highlights that current and local monitoring windows for many sensitive seabird species may be inadequate for making key conservation decisions.

Striking centennial-scale changes in the population size of a threatened seabird.

Many animal populations are under stress and declining. For numerous marine bird species, only recent or sparse monitoring data are available, lacking the appropriate temporal perspective needed to consider natural, long-term population dynamics when developing conservation strategies. Here, we use a combination of established palaeoenvironmental approaches to examine the centennial-scale dynamics of the world's largest colony (representing approx. 50% of the global population) of the declining and vulnerable Leach's Storm-petrel (Hydrobates leucorhous). By reconstructing the last approximately 1700 years of the colony's population trends, we corroborate recent surveys indicating rapid declines since the 1980s. More surprisingly, however, was that the colony size was smaller and has changed strikingly in the past, even prior to the introduction of human stressors. Our results challenge notions that very large colonies are generally stable in the absence of anthropogenic pressures and speak to an increasingly pressing need to better understand inter-colony movement and recruitment when inferring range- and species-wide trends. While the recently documented decline in storm-petrels clearly warrants conservation concern, we show that colony size was consistently much lower in the past and changed markedly in the absence of major anthropogenic activity. In response, we emphasize the need for enlarged protected area networks to maintain natural population cycles, coupled with continued research to identify the driver(s) of the current global seabird decline.

A metabolomics study on effects of polyaromatic compounds in oil sand extracts on the respiratory, hepatic and nervous systems using three human cell lines.

Polyaromatic compounds (PACs) are by-products of combustion and are the major pollutants from the oil and gas industry. However, the mechanism of PACs induced toxicity still remains elusive. The aim of this study was to elucidate the effects of a typical mixture of PACs found in oil sand extract (OSE) on the respiratory, hepatic and nervous systems in humans using in vitro cell culture models followed by non-targeted metabolomics analysis. OSE collected from Alberta, Canada was fractionated into PAC and alkane fractions, and their effects after 24 h exposure on the cell viability measured by MTT assay in three human cell lines (A549, HepG2, and SK-N-SH) were studied. The PAC fractions showed significant dose-dependent cytotoxicity. A549 cells showed the highest sensitivity to OSE extracts, followed by SK-N-SH and HepG2. In contrast, the alkane fractions showed no effects on cell viability. The three human cell lines were further exposed with the PACs at 10% and 20% lethal concentration for 24 h. Metabolomics analysis of the cell extracts indicated that PACs treatments showed different disruptions on possible metabolic pathways on the three cell lines. PACs altered the sex steroid hormone metabolism and regulated the levels of leukotrienes metabolites in all three cell types. The amino acids L-cysteine, L-glutamine, L-tyrosine that are known to cause respiratory effects were significantly up-regulated in A549 cells. The PACs treated HepG2 cells showed down-regulation in metabolites responsible for the inflammatory mediation. Treatment of the differentiated SK-N-SH cells showed up-regulated metabolites involved with butanoate, fatty acid, and pyrimidine metabolism. Leukotriene metabolites were found to be significantly increased in all PACs treated cells. In conclusion, our results showed that PACs in OSE can alter the metabolism of the human lung, liver and neuronal cells and may induce toxicity in multiple target organs.

Sterols and stanols as novel tracers of waterbird population dynamics in freshwater ponds.

With the expansion of urban centres in the mid-twentieth century and the post-1970 decrease in pesticides, populations of double-crested cormorants (Phalacrocorax auritus) and ring-billed gulls (Larus delawarensis) around Lake Ontario (Canada and USA) have rapidly rebounded, possibly to unprecedented numbers. Along with the use of traditional palaeolimnological methods (e.g. stable isotopes, biological proxies), we now have the capacity to develop specific markers for directly tracking the presence of waterbirds on nesting islands. Here, we apply the use of lipophilic sterols and stanols from both plant and animal-faecal origins as a reliable technique, independent of traditional isotopic methods, for pinpointing waterbird arrival and population growth over decadal timescales. Sterol and stanol concentrations measured in the guano samples of waterbird species were highly variable within a species and between the three species of waterbirds examined. However, cholesterol was the dominant sterol in guano, and phytosterols were also high in ring-billed gull guano. This variability highlights a specialist piscivorous diet for cormorants compared to a generalist, omnivorous diet for gulls, which may now often include grain and invertebrates from agricultural fields. A ratio that includes cholesterol and sitosterol plus their aerobically reduced products (cholestanol, stigmastanol) best explained the present range of bird abundance across the islands and was significantly correlated to sedimentary δ15N. Overall, we demonstrate the use of sterols and stanols as a direct means for tracking the spatial and temporal presence of waterbirds on islands across Lake Ontario, and probably elsewhere.

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.

Elevated Exposures to Polycyclic Aromatic Hydrocarbons and Other Organic Mutagens in Ottawa Firefighters Participating in Emergency, On-Shift Fire Suppression.

Occupational exposures to combustion emissions were examined in Ottawa Fire Service (OFS) firefighters. Paired urine and dermal wipe samples (i.e., pre- and post-event) as well as personal air samples and fire event questionnaires were collected from 27 male OFS firefighters. A total of 18 OFS office workers were used as additional controls. Exposures to polycyclic aromatic hydrocarbons (PAHs) and other organic mutagens were assessed by quantification of urinary PAH metabolite levels, levels of PAHs in dermal wipes and personal air samples, and urinary mutagenicity using the Salmonella mutagenicity assay (Ames test). Urinary Clara Cell 16 (CC16) and 15-isoprostane F2t (8-iso-PGF2α) levels were used to assess lung injury and overall oxidative stress, respectively. The results showed significant 2.9- to 5.3-fold increases in average post-event levels of urinary PAH metabolites, depending on the PAH metabolite (p < 0.0001). Average post-event levels of urinary mutagenicity showed a significant, event-related 4.3-fold increase (p < 0.0001). Urinary CC16 and 8-iso-PGF2α did not increase. PAH concentrations in personal air and on skin accounted for 54% of the variation in fold changes of urinary PAH metabolites (p < 0.002). The results indicate that emergency, on-shift fire suppression is associated with significantly elevated exposures to combustion emissions.

Neurotoxicity of alkylated polycyclic aromatic compounds in human neuroblastoma cells.

Polycyclic aromatic compounds (PAC) are ubiquitous environmental pollutants originating from incomplete combustion processes. While the toxicity of parent PAC such as benzo[a]pyrene (BaP) is well characterized, effects of other alkyl-PAC dibenzothiophene (DBT) and retene (Ret) are not well established. The aim of this study was to examine the underlying relative neurotoxic mechanisms attributed to BaP (parent PAH), DBT and Ret (alkyl-PACs) using human neuroblastoma SK-N-SH cells. The lethal concentrations (LC10 and LC20) were found at approximately 10 µM and 40 µM, respectively after 24-h exposure of SK-N-SH cells. It was hypothesized that PAC trigger reactive oxygen species (ROS) production, leading to activation of apoptotic signaling pathways. Differentiated neuronal cells were treated with three compounds at (0.5-40 µM) for 24 h. There was a significant concentration-dependent increase in levels of ROS, even at sub-lethal levels of 1 µM Ret. The mitochondrial membrane potential (MMP) was significantly decreased. Real-time RT-PCR results showed up-regulation of pro-apoptotic genes and down-regulation of antioxidative genes expression in BaP-, DBT-, and Ret-treated SK-N-SH cells. Cytochrome c protein levels and lipid peroxidation (LPO) were also significantly elevated in a concentration-related manner. Data demonstrated that BaP-, DBT-, or Ret-induced neuronal cell damage involved oxidative stress generation through mitochondria-mediated apoptosis pathway. Alkyl-PAC also exhibited higher potency in ROS induction and reduction of MMP than parent PAC. These findings may be important for environmental risk assessment attributed to exposure to PAC.

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.

Sterols and Stanols Preserved in Pond Sediments Track Seabird Biovectors in a High Arctic Environment.

Seabirds are major vertebrates in the coastal ecosystems of the Canadian High Arctic, where they transport substantial amounts of marine-derived nutrients and pollutants from oceans to land by depositing guano and stomach oils to their nesting area, which often includes nearby freshwater ponds. Here we present novel indicators for evaluating the impact of seabirds on freshwater ecosystems. The ratio of cholesterol/(cholesterol + sitosterol) in pond sediments showed significant enrichment near a nesting colony of northern fulmars (Fulmarus glacialis) and was significantly correlated with ornithogenic enrichment of sediment as determined by sedimentary δ(15)N. The sterol ratio was also correlated with several bioaccumulative persistent organic pollutants (POPs), suggesting its usefulness in tracking biovector enrichment of contaminants. Human-derived epicoprostanol was also analyzed in the sediments, and its relationship with an abandoned, prehistoric camp was recorded, suggesting its potential as a tracer of prehistoric human activities in the Arctic. Sterols and stanols preserved in sediments appear to be useful geochemical tools that will inform our understanding of migratory species and the presence of prehistoric human populations in the Arctic, and possibly other animal populations.

Dissolved organic matter kinetically controls mercury bioavailability to bacteria.

Predicting the bioavailability of inorganic mercury (Hg) to bacteria that produce the potent bioaccumulative neurotoxin monomethylmercury remains one of the greatest challenges in predicting the environmental fate and transport of Hg. Dissolved organic matter (DOM) affects mercury methylation due to its influence on cell physiology (as a potential nutrient) and its influence on Hg(II) speciation in solution (as a complexing agent), therefore controlling Hg bioavailability. We assessed the role of DOM on Hg(II) bioavailability to a gram-negative bacterium bioreporter under oxic pseudo- and nonequilibrium conditions, using defined media and field samples spanning a wide range of DOM levels. Our results showed that Hg(II) was considerably more bioavailable under nonequilibrium conditions than when DOM was absent or when Hg(II) and DOM had reached pseudoequilibrium (24 h) prior to cell exposure. Under these enhanced uptake conditions, Hg(II) bioavailability followed a bell shaped curve as DOM concentrations increased, both for defined media and natural water samples, consistent with bioaccumulation results in a companion paper (this issue) observed for amphipods. Experiments also suggest that DOM may not only provide shuttle molecules facilitating Hg uptake, but also alter cell wall properties to facilitate the first steps toward Hg(II) internalization. We propose the existence of a short-lived yet critical time window (<24 h) during which DOM facilitates the entry of newly deposited Hg(II) into aquatic food webs, suggesting that the bulk of mercury incorporation in aquatic food webs would occur within hours following its deposition from the atmosphere.

Dissolved organic carbon thresholds affect mercury bioaccumulation in Arctic lakes.

Dissolved organic carbon (DOC) is known to affect the Hg cycle in aquatic environments due to its overriding influence on complexation, photochemical, and microbial processes, but its role as a mediating factor in the bioaccumulation of Hg in aquatic biota has remained enigmatic. Here, we examined 26 tundra lakes in Canada's western Arctic that span a large gradient of DOC concentrations to show that total Hg (HgT) and methyl mercury (MeHg) accumulation by aquatic invertebrates is defined by a threshold response to Hg-DOC binding. Our results showed that DOC promotes HgT and MeHg bioaccumulation in tundra lakes having low DOC (<8.6 - 8.8 mg C L(-1); DOC threshold concentration, TC) whereas DOC inhibits HgT and MeHg bioaccumulation in lakes having high DOC (>DOC TC), consistent with bioaccumulation results in a companion paper (this issue) using a microbial bioreporter. Chemical equilibrium modeling showed that Hg bioaccumulation factors were elevated when Hg was associated mainly to fulvic acids, but became dramatically reduced when DOC was >8.5 mg C L(-1), at which point Hg was associated primarily with strong binding sites on larger, less bioaccessible humic acids. This study demonstrates that the biological uptake of Hg in lakes is determined by binding thresholds on DOC, a water quality variable predicted to change markedly with future environmental change.

Cancer risk to First Nations' people from exposure to polycyclic aromatic hydrocarbons near in-situ bitumen extraction in Cold Lake, Alberta.

BACKGROUND: The Alberta oil sands are an important economic resource in Canada, but there is growing concern over the environmental and health effects as a result of contaminant releases and exposures. Recent studies have shown a temporal and spatial trend of increased polycyclic aromatic hydrocarbon (PAH) concentrations in sediments and snowpack near the Athabasca oil sands operations (i.e., open pit mines), but thus far similar studies have not been done for the Cold Lake region where steam assisted gravity drainage (in situ) extraction is performed. METHODS: Many PAHs are known mutagenic carcinogens, and this study measured soil and atmospheric concentrations of PAHs in the Cold Lake region to assess the excess lifetime cancer risk posed to the First Nations' inhabitants of the region. Using both deterministic and probabilistic risk assessment methods, excess lifetime cancer risks were calculated for exposures from inhalation or inadvertent soil ingestion. RESULTS: The mean excess cancer risk for First Nations' people through ingestion who engage in traditional wilderness activities in the Cold Lake region was 0.02 new cases per 100,000 with an upper 95% risk level of 0.07 cases per 100,000. Exposure to PAHs via inhalation revealed a maximum excess lifetime cancer risk of less than 0.1 cases per 100,000. CONCLUSIONS: Excess lifetime risk values below 1 case per 100,000 is generally considered negligible, thus our analyses did not demonstrate any significant increases in cancer risks associated with PAH exposures for First Nations people inhabiting the Cold Lake region.

Mercury deposition to lake sediments near historic gold mines in northern Canada.

Mercury (Hg) contamination in aquatic systems can lead to adverse human and environmental health outcomes. Yellowknife, a city in Canada's Northwest Territories, is a historic mining community, with two large gold mines (Giant Mine and Con Mine) that used Hg amalgamation methods to extract gold between ∼1938 and 1960. We analyzed dated sediment cores from 20 small lakes to investigate the spatial and temporal Hg deposition patterns within 50 km of Giant Mine. Breakpoint analysis of the within-lake z-score normalized anthropogenic Hg flux indicates two significant time periods of changing emission rates. The first is a significant increase in Hg deposition rate (∼1925) during the time of gold exploration in the region and onset of Hg amalgamation (1938) and the second is a significant decrease in deposition rate that begins around the time of the cessation of Hg amalgamation at Giant Mine (∼1959). Sediment Hg concentrations exceeded the Canadian Council for Ministers of the Environment Interim Sediment Quality Guideline (ISQG) for Hg (0.17 mg/kg dw) in 55% of the lakes (n = 11) during mining (1948-1999). All lakes within 5 km of the Giant Mine roaster stack exceeded CCME ISQG during mining (n = 8), with a 4-fold increase in total Hg concentration observed during mining at these near-field (<5 km from stack) sites. We observed evidence of enriched Hg in near-field, mid-field, and far-field sites. The elevated sedimentary Hg concentrations during mining in near-field sites would have posed a hazard to human and wildlife health during the height of emissions, however the significant decrease in Hg concentrations since the closure of mines in the region demonstrate the potential for recovery in these aquatic ecosystems.