Understanding Food Web Mercury Accumulation Through Trophic Transfer and Carbon Processing along a River Affected by Recent Run-of-river Dams.

Unlike large dams which favor methylation of Hg in flooded soils over long periods, run-of-river dams are designed to flood a limited area of soils and are therefore not expected to significantly affect mercury (Hg) cycling or carbon processing. We studied the Hg and carbon cycles within food webs from several sectors along the Saint-Maurice River, Quebec, Canada, that differ in how they are influenced by two run-of-river dams and other watershed disturbances. We observed peak Hg concentrations in fish five-year postimpoundment, but these levels were reduced three years after this peak. Methylmercury concentrations in low trophic level fish and invertebrates were related to their carbon source (δ13C) rather than their trophic positions (δ15N). Biomagnification, measured by trophic magnification slopes, was driven mainly by methylmercury concentrations in low-trophic level organisms and environmental factors related to organic matter degradation and Hg-methylation. River sectors, δ13C and δ15N, predicted up to 80% of the variability in food web methylmercury concentrations. The installation of run-of-river dams and the related pondages, in association with other watershed disturbances, altered carbon processing, promoted Hg-methylation and its accumulation at the base of the food web, and led to a temporary increase in Hg levels in fish.

Foraging niche partitioning in sympatric seabird populations.

Sympatric species must sufficiently differentiate aspects of their ecological niche to alleviate complete interspecific competition and stably coexist within the same area. Seabirds provide a unique opportunity to understand patterns of niche segregation among coexisting species because they form large multi-species colonies of breeding aggregations with seemingly overlapping diets and foraging areas. Recent biologging tools have revealed that colonial seabirds can differentiate components of their foraging strategies. Specifically, small, diving birds with high wing-loading may have small foraging radii compared with larger or non-diving birds. In the Gulf of St-Lawrence in Canada, we investigated whether and how niche differentiation occurs in four incubating seabird species breeding sympatrically using GPS-tracking and direct field observations of prey items carried by adults to chicks: the Atlantic puffin (Fratercula arctica), razorbill (Alca torda), common murre (Uria aalge), and black-legged kittiwake (Rissa tridactyla). Although there was overlap at foraging hotspots, all species differentiated in either diet (prey species, size and number) or foraging range. Whereas puffins and razorbills consumed multiple smaller prey items that were readily available closer to the colony, murres selected larger more diverse prey that were accessible due to their deeper diving capability. Kittiwakes compensated for their surface foraging by having a large foraging range, including foraging largely at a specific distant hotspot. These foraging habitat specialisations may alleviate high interspecific competition allowing for their coexistence, providing insight on multispecies colonial living.

Synthesis of Maternal Transfer of Mercury in Birds: Implications for Altered Toxicity Risk.

Maternal transfer is a predominant route of methylmercury (MeHg) exposure to offspring. We reviewed and synthesized published and unpublished data on maternal transfer of MeHg in birds. Using paired samples of females' blood (n = 564) and their eggs (n = 1814) from 26 bird species in 6 taxonomic orders, we conducted a meta-analysis to evaluate whether maternal transfer of MeHg to eggs differed among species and caused differential toxicity risk to embryos. Total mercury (THg) concentrations in eggs increased with maternal blood THg concentrations; however, the proportion of THg transferred from females to their eggs differed among bird taxa and with maternal THg exposure. Specifically, a smaller proportion of maternal THg was transferred to eggs with increasing female THg concentrations. Additionally, the proportion of THg that was transferred to eggs at the same maternal blood THg concentration differed among taxonomic orders, with waterfowl (Anseriformes) transferring up to 382% more THg into their eggs than songbirds (Passeriformes). We provide equations to predict THg concentrations in eggs using female blood THg concentrations, and vice versa, which may help translate toxicity benchmarks across tissues and life stages. Our results indicate that toxicity risk of MeHg can vary among bird taxa due to differences in maternal transfer of MeHg to offspring.

Mercury Concentrations in Double-Crested Cormorant Chicks Across Canada.

Mercury (Hg) biomagnifies in aquatic food chains and can reach high concentrations in fish-eating birds. Spatial patterns of Hg have been found in freshwater ecosystems across Canada for many taxa, including fish and birds. However, it often is challenging to sample a representative population size of adult birds to monitor concentrations of contaminants over a large spatial scale. Moreover, adult birds can migrate and can show a contaminant profile that may not be representative of local resources. The goals of this study were (1) to determine if there was a spatial pattern of Hg concentrations in piscivorous birds, (2) to develop a model to estimate Hg concentrations in breeding adults using chicks as proxy, and (3) to develop predictive equations among non-lethal tissues that are representative of local resources in adults (blood and growing feathers). Double-crested Cormorant (Phalacrocorax auritus) chick growing feathers were sampled at 19 sites across Canada. Adult tissues (freshly grown feathers and blood) were sampled at five of those locations to establish correlations between age classes and between adult tissues. We found an increase in Hg concentrations with latitude up to 50°N followed by a decrease. There was a decrease in Hg concentrations from west to east, which contradicts previous studies. We found a good correlation of Hg concentrations between adults and chicks and among adult tissues. Our study shows that chicks are representative of adults and can be a suitable proxy for monitoring local mercury concentrations across Canada.

Mercury transport and human exposure from global marine fisheries.

Human activities have increased the global circulation of mercury, a potent neurotoxin. Mercury can be converted into methylmercury, which biomagnifies along aquatic food chains and leads to high exposure in fish-eating populations. Here we quantify temporal trends in the ocean-to-land transport of total mercury and methylmercury from fisheries and we estimate potential human mercury intake through fish consumption in 175 countries. Mercury export from the ocean increased over time as a function of fishing pressure, especially on upper-trophic-level organisms. In 2014, over 13 metric tonnes of mercury were exported from the ocean. Asian countries were important contributors of mercury export in the last decades and the western Pacific Ocean was identified as the main source. Estimates of per capita mercury exposure through fish consumption showed that populations in 38% of the 175 countries assessed, mainly insular and developing nations, were exposed to doses of methylmercury above governmental thresholds. Our study shows temporal trends and spatial patterns of Hg transport by fisheries. Given the high mercury intake through seafood consumption observed in several understudied yet vulnerable coastal communities, we recommend a comprehensive assessment of the health exposure risk of those populations.

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and flame retardants in northern gannet (Morus bassanus) eggs from Bonaventure Island, Gulf of St. Lawrence, 1994-2014.

Northern gannet (Morus bassanus) eggs from Bonaventure Island, Québec, Canada, were collected to monitor concentrations of contaminants. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) and non-ortho polychlorinated biphenyls (PCBs) were measured in eggs from 2004 and 2009, and several brominated and nonbrominated flame retardants (FRs) were measured every 2-5 years in eggs from 1994 to 2014. The sum (Σ) concentrations of PCDDs/Fs were significantly lower in 2009 relative to 2004, but the total toxic equivalent concentrations for PCDDs, PCDFs, and PCBs showed no significant differences (196 ng/kg wet weight (ww) in 2004 and 220 ng/kg ww in 2009). The mean ΣFR concentrations decreased significantly between 1994 and 2014, from 58 ng/g ww to 19 ng/g ww. Hexabromocyclododecane (HBCDD) was the principal nonbrominated FR detected in gannet eggs and ranged from <1.0 ng/g ww to 6.9 ng/g ww. The PCDD/F and nonortho PCB profiles were dominated by 2,3,7,8- tetrachloro-dibenzofuran (2,3,7,8-TCDF; from 26.2 ng/g ww to 34.8 ng/kg ww) and PCB-77 (from 1580 ng/g ww to 2650 ng/kg ww), respectively. Although the values of both ecological tracer stable isotopes of carbon (δ13C) and nitrogen (δ15N) showed differences among the years, no temporal trends were observed, which indicates relatively stable adults' diet and foraging area over this time period. The trends over time in concentrations of the studied contaminants likely reflect a decrease in environmental contamination. The mean 2012 eggshell thickness was 10% lower than the pre-DDT value and corresponded to a year of poor reproductive success.

Perfluoroalkylphosphinic Acids in Northern Pike (Esox lucius), Double-Crested Cormorants (Phalacrocorax auritus), and Bottlenose Dolphins (Tursiops truncatus) in Relation to Other Perfluoroalkyl Acids.

Perfluoroalkyl phosphinic acids (PFPIAs) are perfluoroalkyl acids (PFAAs) that are used for their surfactant properties in a variety of applications, resulting in their presence in environmental waters; however, they have not been widely studied in biota. A survey of PFPIAs was conducted in fish, dolphins, and birds from various locations in North America. Northern pike (Esox lucius) were collected at two locations in 2011 near Montréal Island in the St. Lawrence River, Canada, double-crested cormorants (Phalacrocorax auritus) were collected from bird colonies in the Great Lakes in 2010-2012, and bottlenose dolphins (Tursiops truncatus) from Sarasota Bay, FL and Charleston Harbor, SC were sampled in 2004-2009. PFPIAs had a detection frequency of 100% in all animals. This is the first report of PFPIAs in fish, dolphin, and bird plasma. Total PFPIA levels (mean ± standard deviation, 1.87 ± 2.17 ng/g wet weight (ww), range of 0.112-15.3 ng/g ww) were 1-2 orders of magnitude lower than those of perfluoroalkyl carboxylates (PFCA) and perfluoroalkanesulfonates (PFSA) in the same samples. The predominant congeners were 6:8 PFPIA (cormorants and pike) and 6:6 PFPIA (dolphins). Total PFPIAs in cormorants from Hamilton Harbour (5.02 ± 2.80 ng/g ww) were statistically higher than in other areas and taxonomic groups. The ubiquity of PFPIAs warrants further research on sources and effects of these unique compounds.

Tracking overwintering areas of fish-eating birds to identify mercury exposure.

Migration patterns are believed to greatly influence concentrations of contaminants in birds due to accumulation in spatially and temporally distinct ecosystems. Two species of fish-eating birds, the Double-crested Cormorant (Phalacrocorax auritus) and the Caspian Tern (Hydroprogne caspia) breeding in Lake Ontario were chosen to measure the impact of overwintering location on mercury concentrations ([Hg]). We characterized (1) overwintering areas using stable isotopes of hydrogen (δ(2)H) and band recoveries, and (2) overwintering habitats by combining information from stable isotopes of sulfur (δ(34)S), carbon (δ(13)C), nitrogen (δ(15)N), and δ(2)H in feathers grown during the winter. Overall, overwintering location had a significant effect on [Hg]. Both species showed high [Hg] in (13)C-rich habitats. In situ production of Hg (e.g., through sulfate reducing bacteria in sediments) and allochthonous import could explain high [Hg] in birds visiting (13)C-rich habitats. Higher [Hg] were found in birds with high δ(2)H, suggesting that Hg is more bioavailable in southern overwintering locations. Hotspot maps informed that higher [Hg] in birds were found at the limit of their southeastern overwintering range. Mercury concentrations in winter feathers were positively related to predicted spatial pattern of [Hg] in fish using the National Descriptive Model of Mercury in Fish (NDMMF) based on bird spatial assignment (using δ(2)H). This study indicates that the overwintering location greatly influences [Hg].

Temporal trends of mercury, organochlorines and PCBs in northern gannet (Morus bassanus) eggs from Bonaventure Island, Gulf of St. Lawrence, 1969-2009.

Since 1969, northern gannet (Morus bassanus) eggs from Bonaventure Island, Québec, have been collected to monitor concentrations of contaminants. Levels of p,p'-DDE, which caused low breeding success of Bonaventure gannets in the 1960s, decreased by 99.4% from 1969 to 2009 (17.1-0.1 mg/kg ww), with concomitant improvement of hatching success. PCBs, most organochlorines and mercury also showed decreasing trends. Stable isotopes of carbon (δ(13)C) and nitrogen (δ(15)N) were measured to track the possible influence of diet changes on concentrations of contaminants over time. The confounding effect of the combustion of fossil fuels on baseline values of δ(13)C (the Suess effect) was taken into account. No temporal trends were observed in δ(13)C and δ(15)N values in gannet eggs. Hence trophic level or foraging area had a negligible influence on temporal trends of contaminants.

Contamination of mercury during the wintering period influences concentrations at breeding sites in two migratory piscivorous birds.

Many aquatic fish-eating birds migrate long distances and are exposed to different mercury concentrations ([Hg]) during their annual cycle. Here we examined the importance of migration on [Hg] in two colonial migratory fish-eating bird species. We determined temporal trends of [Hg] and stable isotopes of carbon (δ(13)C) and nitrogen (δ(15)N) during the annual cycle in Double-crested Cormorants (Phalacrocorax auritus) and Caspian Terns (Hydroprogne caspia) breeding in Lake Ontario by a repeated sampling of breast feathers and blood from recaptured individuals. We found an effect of previous winter [Hg], species, sex, and location to explain variations of Hg at breeding sites. This suggests Hg carryover from winter to summer periods and that variations of [Hg] in the summer are partially explained by [Hg] in the winter. Carryover of Hg among seasons and slow changes in [Hg] over time were found especially for individuals in high winter exposure groups, suggesting a slow depuration rate and a fast uptake rate for both species. In contrast, stable isotope values rapidly switched to reach equilibrium at a similar midpoint regardless of winter habitat or diet suggesting minimal carryover of isotopic signatures. The potential of Hg carryover from wintering sites indicates that Hg concentrations in birds at a given time may be influenced by previous exposure from distant locations.

A positive correlation between mercury and oxidative stress-related gene expression (GPX3 and GSTM3) is measured in female Double-crested Cormorant blood.

Mercury (Hg) is a widespread contaminant that has been shown to induce a wide range of adverse health effects in birds including reproductive, physiological and neurological impairments. Here we explored the relationship between blood total Hg concentrations ([THg]) and oxidative stress gene induction in the aquatic piscivorous Double-crested Cormorants (Phalacrocorax auritus) using a non-lethal technique, i.e., blood gene expression analysis. P. auritus blood was sampled at five sites across the Great Lakes basin, Ontario, Canada and was analyzed for [THg]. To assess cellular stress, the expression of glutathione peroxidases 1 and 3 (GPX1, GPX3), superoxide dismutase 1 (SOD1), heat-shock protein 70 kd-8 (HSP70-8) and glutathione S-transferase µ3 (GSTM3) were measured in whole blood samples using real-time RT-PCR. Results showed a significantly positive correlation between female blood [THg] and both GPX3 and GSTM3 expression. Different levels of oxidative stress experienced by males and females during the breeding season may be influencing the differential oxidative stress responses to blood [THg] observed in this study. Overall, these results suggest that Hg may lead to oxidative stress as some of the cellular stress-related genes were altered in the blood of female P. auritus and that blood gene expression analysis is a successful approach to assess bird health condition.

Biomagnification of mercury in aquatic food webs: a worldwide meta-analysis.

The slope of the simple linear regression between log10 transformed mercury (Hg) concentration and stable nitrogen isotope values (δ(15)N), hereafter called trophic magnification slope (TMS), from several trophic levels in a food web can represent the overall degree of Hg biomagnification. We compiled data from 69 studies that determined total Hg (THg) or methyl Hg (MeHg) TMS values in 205 aquatic food webs worldwide. Hg TMS values were compared against physicochemical and biological factors hypothesized to affect Hg biomagnification in aquatic systems. Food webs ranged across 1.7 ± 0.7 (mean ± SD) and 1.8 ± 0.8 trophic levels (calculated using δ(15)N from baseline to top predator) for THg and MeHg, respectively. The average trophic level (based on δ(15)N) of the upper-trophic-level organisms in the food web was 3.7 ± 0.8 and 3.8 ± 0.8 for THg and MeHg food webs, respectively. For MeHg, the mean TMS value was 0.24 ± 0.08 but varied from 0.08 to 0.53 and was, on average, 1.5 times higher than that for THg with a mean of 0.16 ± 0.11 (range: -0.19 to 0.48). Both THg and MeHg TMS values were significantly and positively correlated with latitude. TMS values in freshwater sites increased with dissolved organic carbon and decreased with total phosphorus and atmospheric Hg deposition. Results suggest that Hg biomagnification through food webs is highest in cold and low productivity systems; however, much of the among-system variability in TMS values remains unexplained. We identify critical data gaps and provide recommendations for future studies that would improve our understanding of global Hg biomagnification.

Trophic structure and mercury distribution in a Gulf of St. Lawrence (Canada) food web using stable isotope analysis.

Even at low concentrations in the environment, mercury has the potential to biomagnify in food chains and reaches levels of concern in apex predators. The aim of this study was to relate the transfer of total mercury (THg) and methylmercury (MeHg) in a Gulf of St. Lawrence food web to the trophic structure, from primary consumers to seabirds, using stable nitrogen (δ(15)N) and carbon (δ(13)C) isotope analysis and physical environmental parameters. The energy reaching upper trophic level species was principally derived from pelagic primary production, with particulate organic matter (POM) at the base of the food chain. We developed a biomagnification factor (BMF) taking into account the various prey items consumed by a given predator using stable isotope mixing models. This BMF provides a more realistic estimation than when using a single prey. Lipid content, body weight, trophic level and benthic connection explained 77.4 and 80.7% of the variation in THg and MeHg concentrations, respectively in this food web. When other values were held constant, relationships with lipid and benthic connection were negative whereas relationships with trophic level and body weight were positive. Total Hg and MeHg biomagnified in this food web with biomagnification power values (slope of the relationship with δ(15)N) of 0.170 and 0.235, respectively on wet weight and 0.134 and 0.201, respectively on dry weight. Values of biomagnification power were greater for pelagic and benthopelagic species compared to benthic species whereas the opposite trend was observed for levels at the base of the food chain. This suggests that Hg would be readily bioavailable to organisms at the base of the benthic food chain, but trophic transfer would be more efficient in each trophic level of pelagic and benthopelagic food chains.

Organochlorines, brominated flame retardants and mercury levels in six seabird species from the Gulf of St. Lawrence (Canada): relationships with feeding ecology, migration and molt.

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (delta15N) and carbon (delta13C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (SigmaPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (SigmaCPs), the sum of brominated flame retardants (SigmaBFRs) and finally total Hg (THg). SigmaPCBs, SigmaCPs and SigmaBFRs increased with trophic level, whereas THg did not. Only SigmaBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.