Seabirds reveal mercury distribution across the North Atlantic.

Mercury (Hg) is a heterogeneously distributed toxicant affecting wildlife and human health. Yet, the spatial distribution of Hg remains poorly documented, especially in food webs, even though this knowledge is essential to assess large-scale risk of toxicity for the biota and human populations. Here, we used seabirds to assess, at an unprecedented population and geographic magnitude and high resolution, the spatial distribution of Hg in North Atlantic marine food webs. To this end, we combined tracking data of 837 seabirds from seven different species and 27 breeding colonies located across the North Atlantic and Atlantic Arctic together with Hg analyses in feathers representing individual seabird contamination based on their winter distribution. Our results highlight an east-west gradient in Hg concentrations with hot spots around southern Greenland and the east coast of Canada and a cold spot in the Barents and Kara Seas. We hypothesize that those gradients are influenced by eastern (Norwegian Atlantic Current and West Spitsbergen Current) and western (East Greenland Current) oceanic currents and melting of the Greenland Ice Sheet. By tracking spatial Hg contamination in marine ecosystems and through the identification of areas at risk of Hg toxicity, this study provides essential knowledge for international decisions about where the regulation of pollutants should be prioritized.

Blood Kinetics of Lipophilic and Proteinophilic Pollutants during Two Types of Long-Term Fast in King Penguins.

In vertebrates, fasting is an intricate physiological process associated with strong metabolic changes, yet its effect on pollutant residue variation is poorly understood. Here, we quantified long-term changes in plasma concentrations of 20 organochlorine and 16 perfluoroalkyl pollutants in king penguins Aptenodytes patagonicus during the breeding and molting fasts, which are marked by low and high levels of protein catabolism, respectively, and by strong lipid use. The profile of measured pollutants in plasma was dominated by perfluorooctanesulfonic acid (PFOS, initial relative contribution of 60%). Initial total pollutant concentrations were similar in molting (3.3-5.7 ng g-1 ww) and breeding penguins (range of 4.2-7.3 ng g-1 wet weight, ww). Long-term fasting (25 days) for molting and breeding led, respectively, to a 1.8- and 2.2-fold increase in total plasma pollutant concentrations, although the rate and direction of change were compound-specific. Hexachlorbenzene (HCB) and PFOS concentrations increased in plasma (net mobilization) during both types of fasting, likely due to lipid use. Plasma perfluoroundecanoate (PFUnDA) and perfluorotridecanoate (PFTrDA) concentrations increased in breeders (net mobilization) but decreased in molting individuals (net excretion), suggesting a significant incorporation of these pollutants into feathers. This study is a key contribution to our understanding of pollutant variation in blood during long-term fasting in wildlife.

Global mercury concentrations in biota: their use as a basis for a global biomonitoring framework.

An important provision of the Minamata Convention on Mercury is to monitor and evaluate the effectiveness of the adopted measures and its implementation. Here, we describe for the first time currently available biotic mercury (Hg) data on a global scale to improve the understanding of global efforts to reduce the impact of Hg pollution on people and the environment. Data from the peer-reviewed literature were compiled in the Global Biotic Mercury Synthesis (GBMS) database (>550,000 data points). These data provide a foundation for establishing a biomonitoring framework needed to track Hg concentrations in biota globally. We describe Hg exposure in the taxa identified by the Minamata Convention: fish, sea turtles, birds, and marine mammals. Based on the GBMS database, Hg concentrations are presented at relevant geographic scales for continents and oceanic basins. We identify some effective regional templates for monitoring methylmercury (MeHg) availability in the environment, but overall illustrate that there is a general lack of regional biomonitoring initiatives around the world, especially in Africa, Australia, Indo-Pacific, Middle East, and South Atlantic and Pacific Oceans. Temporal trend data for Hg in biota are generally limited. Ecologically sensitive sites (where biota have above average MeHg tissue concentrations) have been identified throughout the world. Efforts to model and quantify ecosystem sensitivity locally, regionally, and globally could help establish effective and efficient biomonitoring programs. We present a framework for a global Hg biomonitoring network that includes a three-step continental and oceanic approach to integrate existing biomonitoring efforts and prioritize filling regional data gaps linked with key Hg sources. We describe a standardized approach that builds on an evidence-based evaluation to assess the Minamata Convention's progress to reduce the impact of global Hg pollution on people and the environment.

Mercury Concentrations in Feathers of Albatrosses and Large Petrels at South Georgia: Contemporary Patterns and Comparisons with Past Decades.

Mercury (Hg) is an environmental contaminant that can negatively impact the health of humans and wildlife. Albatrosses and large petrels show some of the highest levels of Hg contamination among birds, with potential repercussions for reproduction and survival. Here, body feather total Hg (THg) concentrations were determined in breeding adults of five species of albatrosses and large petrels in the foraging guild at South Georgia during the mid-2010s. We tested the effects of species, sex and trophic ecology (inferred from stable isotopes) on THg concentrations and compared our results with published values from past decades. Feather THg concentrations differed significantly among species (range: 1.9-49.6 µg g-1 dw), and were highest in wandering albatrosses Diomedea exulans, intermediate in black-browed albatrosses Thalassarche melanophris and northern giant petrels Macronectes halli, and lowest in southern giant petrels M. giganteus and white-chinned petrels Procellaria aequinoctialis. Females were more contaminated than males in all species, potentially due to differences in distributions and diet composition. Across species, THg concentrations were not correlated with feather δ13C or δ15N values, implying that species effects (e.g., breeding and moulting frequencies) may be more important than trophic effects in explaining feather THg concentrations in this foraging guild. Within species, the only significant correlation was between THg and δ13C in wandering albatrosses, which could reflect higher Hg exposure in subtropical waters. Comparisons with THg concentrations from past studies, which reflect contamination from 10 to > 60 years ago, revealed considerable annual variation and some evidence for increases over time for wandering and black-browed albatrosses since before 1950 and from the late 1980s, respectively.

In Vivo Mercury (De)Methylation Metabolism in Cephalopods under Different pCO2 Scenarios.

This work quantified the accumulation efficiencies of Hg in cuttlefish, depending on both organic (MeHg) and inorganic (Hg(II)) forms, under increased pCO2 (1600 µatm). Cuttlefish were fed with live shrimps injected with two Hg stable isotopic tracers (Me202Hg and 199Hg(II)), which allowed for the simultaneous quantification of internal Hg accumulation, Hg(II) methylation, and MeHg demethylation rates in different organs. Results showed that pCO2 had no impact on Hg bioaccumulation and organotropism, and both Hg and pCO2 did not influence the microbiota diversity of gut and digestive gland. However, the results also demonstrated that the digestive gland is a key organ for in vivo MeHg demethylation. Consequently, cuttlefish exposed to environmental levels of MeHg could exhibit in vivo MeHg demethylation. We hypothesize that in vivo MeHg demethylation could be due to biologically induced reactions or to abiotic reactions. This has important implications as to how some marine organisms may respond to future ocean change and global mercury contamination.

Mercury Contamination Challenges the Behavioral Response of a Keystone Species to Arctic Climate Change.

Combined effects of multiple, climate change-associated stressors are of mounting concern, especially in Arctic ecosystems. Elevated mercury (Hg) exposure in Arctic animals could affect behavioral responses to changes in foraging landscapes caused by climate change, generating interactive effects on behavior and population resilience. We investigated this hypothesis in little auks (Alle alle), a keystone Arctic seabird. We compiled behavioral data for 44 birds across 5 years using accelerometers while also quantifying blood Hg and environmental conditions. Warm sea surface temperature (SST) and low sea ice coverage reshaped time activity budgets (TABs) and diving patterns, causing decreased resting, increased flight, and longer dives. Mercury contamination was not associated with TABs. However, highly contaminated birds lengthened interdive breaks when making long dives, suggesting Hg-induced physiological limitations. As dive durations increased with warm SST, subtle toxicological effects threaten to increasingly constrain diving and foraging efficiency as climate change progresses, with ecosystem-wide repercussions.

Trace elements, dioxins and PCBs in different fish species and marine regions: Importance of the taxon and regional features.

Chemical contaminant concentrations in wild organisms are used to assess environmental status under the European Marine Strategy Framework Directive. However, this approach is challenged by the complex intra- and inter-species variability, and the different regional features. In this study, concentrations in trace elements (As, Cd, Hg and Pb), polychlorinated biphenyls (PCBs), polychlorodibenzo-para-dioxines (PCDDs) and polychlorodibenzofuranes (PCDFs) were monitored in 8 fish species sampled on the continental shelf of three French regions: the Eastern English Channel (EEC) and Bay of Biscay (BoB) in the Northeast Atlantic Ocean, and the Gulf of Lions (GoL) in Western Mediterranean Sea. Our objectives were to identify species or regions more likely to be contaminated and to assess how to take this variability into account in environmental assessment. While concentrations were higher in benthic and demersal piscivores, PCB and PCDD/F concentrations (lipid-weight) were similar in most teleost species. For Cd, Hg and Pb, the trophic group accumulating the highest concentrations depended on the contaminant and region. Concentrations in Hg, PCBs and PCDD/Fs were higher in the EEC and/or GoL than in BoB. Cadmium and Pb concentrations were highest in the BoB. Lipid content accounted for 35%-84% of organic contaminant variability. Lipid normalisation was employed to enhance robustness in the identification of spatial patterns. Contaminant patterns in chondrichthyans clearly differed from that in teleosts. In addition, trophic levels accounted for ≤1% and ≤33% of the contaminant variability in teleost fishes in the EEC and BoB, respectively. Therefore, developing taxa-specific thresholds might be a more practical way forward for environmental assessment than normalisation to trophic levels.

Do foraging ecology and contaminants interactively predict parenting hormone levels in common eider?

Global climate change is causing abiotic shifts such as higher air and ocean temperatures, and disappearing sea ice in Arctic ecosystems. These changes influence Arctic-breeding seabird foraging ecology by altering prey availability and selection, affecting individual body condition, reproductive success, and exposure to contaminants such as mercury (Hg). The cumulative effects of alterations to foraging ecology and Hg exposure may interactively alter the secretion of key reproductive hormones such as prolactin (PRL), important for parental attachment to eggs and offspring and overall reproductive success. However, more research is needed to investigate the relationships between these potential links. Using data collected from 106 incubating female common eiders (Somateria mollissima) at six Arctic and sub-Arctic colonies, we examined whether the relationship between individual foraging ecology (assessed using δ13C, δ15N) and total Hg (THg) exposure predicted PRL levels. We found a significant, complex interaction between δ13C, δ15N and THg on PRL, suggesting that individuals cumulatively foraging at lower trophic levels, in phytoplankton-dominant environments, and with the highest THg levels had the most constant significant relationship PRL levels. Cumulatively, these three interactive variables resulted in lowered PRL. Overall, results demonstrate the potential downstream and cumulative implications of environmentally induced changes in foraging ecology, in combination with THg exposure, on hormones known to influence reproductive success in seabirds. These findings are notable in the context of continuing environmental and food web changes in Arctic systems, which may make seabird populations more susceptible to ongoing stressors.

Mercury contamination in the tropical seabird community from Clipperton Island, eastern Pacific Ocean.

Mercury (Hg) pollution is a global problem affecting remote areas of the open ocean, but the bioaccumulation of this neurotoxic pollutant in tropical top predators remains poorly documented. The objective of this study was to determine Hg contamination of the seabird community nesting on Clipperton Island using blood and feathers to investigate short and longer-term contamination, respectively. We examined the significance of various factors (species, sex, feeding habitat [δ13C] and trophic position [δ15N]) on Hg concentrations in six seabird species. Among species, Great Frigatebirds had the highest Hg concentrations in blood and feathers, boobies had intermediate values, and Brown Noddies and Sooty Terns the lowest. At the interspecific level, although δ13C values segregated boobies from frigatebirds and noddies/terns, Hg concentrations were explained by neither δ13C nor δ15N values. At the intraspecific level, both Hg concentrations in blood and feathers show relatively small variations (16-32 and 26-74%, respectively), suggesting that feeding ecology had low seasonal variation among individuals. Despite most species being sexually dimorphic, differences in Hg contamination according to sex was detected only in Brown Boobies during the breeding period. Indeed, female Brown Boobies feed at a higher trophic level and in a different area than males during this period, resulting in higher blood Hg concentrations. The present study also shows that most of the seabirds sampled at Clipperton Island had little or no exposure to Hg toxicity, with 30% in the no risk category and 70% in the low risk category.

Circumpolar assessment of mercury contamination: the Adélie penguin as a bioindicator of Antarctic marine ecosystems.

Due to its persistence and potential ecological and health impacts, mercury (Hg) is a global pollutant of major concern that may reach high concentrations even in remote polar oceans. In contrast to the Arctic Ocean, studies documenting Hg contamination in the Southern Ocean are spatially restricted and large-scale monitoring is needed. Here, we present the first circumpolar assessment of Hg contamination in Antarctic marine ecosystems. Specifically, the Adélie penguin (Pygoscelis adeliae) was used as a bioindicator species, to examine regional variation across 24 colonies distributed across the entire Antarctic continent. Mercury was measured on body feathers collected from both adults (n = 485) and chicks (n = 48) between 2005 and 2021. Because penguins' diet represents the dominant source of Hg, feather δ13C and δ15N values were measured as proxies of feeding habitat and trophic position. As expected, chicks had lower Hg concentrations (mean ± SD: 0.22 ± 0.08 µg·g‒1) than adults (0.49 ± 0.23 µg·g‒1), likely because of their shorter bioaccumulation period. In adults, spatial variation in feather Hg concentrations was driven by both trophic ecology and colony location. The highest Hg concentrations were observed in the Ross Sea, possibly because of a higher consumption of fish in the diet compared to other sites (krill-dominated diet). Such large-scale assessments are critical to assess the effectiveness of the Minamata Convention on Mercury. Owing to their circumpolar distribution and their ecological role in Antarctic marine ecosystems, Adélie penguins could be valuable bioindicators for tracking spatial and temporal trends of Hg across Antarctic waters in the future.

Mercury in Ten Storm-Petrel Populations from the Antarctic to the Subtropics.

The oceans become increasingly contaminated as a result of global industrial production and consumer behaviour, and this affects wildlife in areas far removed from sources of pollution. Migratory seabirds such as storm-petrels may forage in areas with different contaminant levels throughout the annual cycle and may show a carry-over of mercury from the winter quarters to the breeding sites. In this study, we compared mercury levels among seven species of storm-petrels breeding on the Antarctic South Shetlands and subantarctic Kerguelen Islands, in temperate waters of the Chatham Islands, New Zealand, and in temperate waters of the Pacific off Mexico. We tested for differences in the level of contamination associated with breeding and inter-breeding distribution and trophic position. We collected inert body feathers and metabolically active blood samples in ten colonies, reflecting long-term (feathers) and short-term (blood) exposures during different periods ranging from early non-breeding (moult) to late breeding. Feathers represent mercury accumulated over the annual cycle between two successive moults. Mercury concentrations in feathers ranged over more than an order of magnitude among species, being lowest in subantarctic Grey-backed Storm-petrels (0.5 µg g-1 dw) and highest in subtropical Leach's Storm-petrels (7.6 µg g-1 dw, i.e. posing a moderate toxicological risk). Among Antarctic Storm-petrels, Black-bellied Storm-petrels had threefold higher values than Wilson's Storm-petrels, and in both species, birds from the South Shetlands (Antarctica) had threefold higher values than birds from Kerguelen (subantarctic Indian Ocean). Blood represents mercury taken up over several weeks, and showed similar trends, being lowest in Grey-backed Storm-petrels from Kerguelen (0.5 µg g-1 dw) and highest in Leach's Storm-petrels (3.6 µg g-1 dw). Among Antarctic storm-petrels, species differences in the blood samples were similar to those in feathers, but site differences were less consistent. Over the breeding season, mercury decreased in blood samples of Antarctic Wilson's Storm-petrels, but did not change in Wilson's Storm-petrels from Kerguelen or in Antarctic Black-bellied Storm-petrels. In summary, we found that mercury concentrations in storm-petrels varied due to the distribution of species and differences in prey choice. Depending on prey choices, Antarctic storm-petrels can have similar mercury concentrations as temperate species. The lowest contamination was observed in subantarctic species and populations. The study shows how seabirds, which accumulate dietary pollutants in their tissues in the breeding and non-breeding seasons, can be used to survey marine pollution. Storm-petrels with their wide distributions and relatively low trophic levels may be especially useful, but more detailed knowledge on their prey choice and distributions is needed.

Is bedding material a more effective thermal insulator than trap cover for small mammal trapping? A field experiment.

Live trapping is a key technique for conducting ecological studies on small mammals. All-metal live traps are popular in monitoring schemes owing to their tested performance, lightweight design (aluminium) and foldability. However, capture represents a stressful situation for small mammals, particularly during cold seasons, when individuals are susceptible to cold weather starvation resulting from low temperature and insufficient food to maintain body temperature. Metal live traps provide limited protection against cold temperatures, and it is often recommended to use covers to buffer external temperature fluctuations and prevent entry of moisture. Here, we compared the insulative performance of a PVC cover designed for Sherman traps and of bedding material, using data loggers to record temperature and humidity inside traps. We conducted different experiments simulating field conditions (traps at night with a heat source inside) and different treatments (cover, bedding material) to test the thermal insulation capacity of three models of widely used commercial traps: Longworth, Sherman, and Heslinga. Our findings indicated that Longworth and Sherman traps were better insulated against ambient air temperature fluctuations than Heslinga traps (+2.0 °C warmer on average). Bedding material was paramount in reducing relative humidity and increasing thermal insulation capacity of traps (+3.1 °C), an effect that was strengthened when a PVC cover was additionally used (+4.2 °C). The covered traps prevented the direct entrance of rain and dew (reducing damp bedding), provided camouflage (reducing thefts), and improved thermal and humidity conditions of traps (potentially increasing survival of captive small mammals). Our results suggest that using covers and bedding materials can improve thermal and humidity conditions within live traps, thus reducing the metabolic costs of thermoregulation and increasing survival chances for trapped small mammals during cold seasons.

A U-Turn for Mercury Concentrations over 20 Years: How Do Environmental Conditions Affect Exposure in Arctic Seabirds?

Mercury (Hg) is highly toxic in its methylated form (MeHg), and global change is likely to modify its bioavailability in the environment. However, it is unclear how top predators will be impacted. We studied blood Hg concentrations of chick-rearing black-legged kittiwakes Rissa tridactyla (2000-2019) in Svalbard (Norway). From 2000 to 2019, Hg concentrations followed a U-shaped trend. The trophic level, inferred from nitrogen stable isotopes, and chlorophyll a (Chl a) concentrations better predicted Hg concentrations, with positive and U-shaped associations, respectively. As strong indicators of primary productivity, Chl a concentrations can influence production of upper trophic levels and, thus, fish community assemblage. In the early 2000s, the high Hg concentrations were likely related to a higher proportion of Arctic prey in kittiwake's diet. The gradual input of Atlantic prey in kittiwake diet could have resulted in a decrease in Hg concentrations until 2013. Then, a new shift in the prey community, added to the shrinking sea ice-associated release of MeHg in the ocean, could explain the increasing trend of Hg observed since 2014. The present monitoring provides critical insights about the exposure of a toxic contaminant in Arctic wildlife, and the reported increase since 2014 raises concern for Arctic seabirds.

First Time Identification of Selenoneine in Seabirds and Its Potential Role in Mercury Detoxification.

Birds are principally exposed to selenium (Se) through their diet. In long-lived and top predator seabirds, such as the giant petrel, extremely high concentrations of Se are found. Selenium speciation in biota has aroused great interest in recent years; however, there is a lack of information about the chemical form of Se in (sea)birds. The majority of publications focus on the growth performance and antioxidant status in broilers in relation to Se dietary supplementation. The present work combines elemental and molecular mass spectrometry for the characterization of Se species in wild (sea)birds. A set of eight giant petrels (Macronectes sp.) with a broad age range from the Southern Ocean were studied. Selenoneine, a Se-analogue of ergothioneine, was identified for the first time in wild avian species. This novel Se-compound, previously reported in fish, constitutes the major Se species in the water-soluble fraction of all of the internal tissues and blood samples analyzed. The levels of selenoneine found in giant petrels are the highest reported in animal tissues until now, supporting the trophic transfer in the marine food web. The characterization of selenoneine in the brain, representing between 78 and 88% of the total Se, suggests a crucial role in the nervous system. The dramatic decrease of selenoneine (from 68 to 3%) with an increase of Hg concentrations in the liver strongly supports the hypothesis of its key role in Hg detoxification.

Stage-dependent niche segregation: insights from a multi-dimensional approach of two sympatric sibling seabirds.

Niche theory predicts that to reduce competition for the same resource, sympatric ecologically similar species should exploit divergent niches and segregate in one or more dimensions. Seasonal variations in environmental conditions and energy requirements can influence the mechanisms and the degree of niche segregation. However, studies have overlooked the multi-dimensional aspect of niche segregation over the whole annual cycle, and key facets of species co-existence still remain ambiguous. The present study provides insights into the niche use and partitioning of two morphologically and ecologically similar seabirds, the common (CDP, Pelecanoides urinatrix) and the South Georgian diving petrel (SGDP, Pelecanoides georgicus). Using phenology, at-sea distribution, diving behavior and isotopic data (during the incubation, chick-rearing and non-breeding periods), we show that the degree of partitioning was highly stage-dependent. During the breeding season, the greater niche segregation during chick-rearing than incubation supported the hypothesis that resource partitioning increases during energetically demanding periods. During the post breeding period, while species-specific latitudinal differences were expected (species specific water mass preference), CDP and SGDP also migrated in divergent directions. This segregation in migration area may not be only a response to the selective pressure arising from competition avoidance between sympatric species, but instead, could reflect past evolutionary divergence. Such stage-dependent and context-dependent niche segregation demonstrates the importance of integrative approaches combining techniques from different fields, throughout the entire annual cycle, to better understand the co-existence of ecologically similar species. This is particularly relevant in order to fully understand the short and long-term effects of ongoing environmental changes on species distributions and communities.This work demonstrates the need of integrative multi-dimensional approaches combining concepts and techniques from different fields to understand the mechanism and causal factors of niche segregation.

Bioaccumulation of inorganic and organic mercury in the cuttlefish Sepia officinalis: Influence of ocean acidification and food type.

The bioaccumulation of mercury (Hg) in marine organisms through various pathways has not yet been fully explored, particularly in cephalopods. This study utilises radiotracer techniques using the isotope 203Hg to investigate the toxicokinetics and the organotropism of waterborne inorganic Hg (iHg) and dietary inorganic and organic Hg (methylHg, MeHg) in juvenile common cuttlefish Sepia officinalis. The effect of two contrasting CO2 partial pressures in seawater (400 and 1600 µatm, equivalent to pH 8.08 and 7.54, respectively) and two types of prey (fish and shrimp) were tested as potential driving factors of Hg bioaccumulation. After 14 days of waterborne exposure, juvenile cuttlefish showed a stable concentration factor of 709 ± 54 and 893 ± 117 at pH 8.08 and 7.54, respectively. The accumulated dissolved i203Hg was depurated relatively rapidly with a radiotracer biological half-life (Tb1/2) of 44 ± 12 and 55 ± 16 days at pH 8.08 and 7.54, respectively. During the whole exposure period, approximately half of the i203Hg was found in the gills, but i203Hg also increased in the digestive gland. When fed with 203Hg-radiolabelled prey, cuttlefish assimilated almost all the Hg provided (>95%) independently of the prey type. Nevertheless, the prey type played a major role on the depuration kinetics with Hg Tb1/2 approaching infinity in fish fed cuttlefish vs. 25 days in shrimp fed cuttlefish. Such a difference is explained by the different proportion of Hg species in the prey, with fish prey containing more than 80% of MeHg vs. only 30% in shrimp. Four days after ingestion of radiolabelled food, iHg was primarily found in the digestive organs while MeHg was transferred towards the muscular tissues. No significant effect of pH/pCO2 variation was observed during both the waterborne and dietary exposures on the bioaccumulation kinetics and tissue distribution of i203Hg and Me203Hg. Dietary exposure is the predominant pathway of Hg bioaccumulation in juvenile cuttlefish.

Quantifying capital versus income breeding: New promise with stable isotope measurements of individual amino acids.

Capital breeders accumulate nutrients prior to egg development, then use these stores to support offspring development. In contrast, income breeders rely on local nutrients consumed contemporaneously with offspring development. Understanding such nutrient allocations is critical to assessing life-history strategies and habitat use. Despite the contrast between these strategies, it remains challenging to trace nutrients from endogenous stores or exogenous food intake into offspring. Here, we tested a new solution to this problem. Using tissue samples collected opportunistically from wild emperor penguins Aptenodytes forsteri, which exemplify capital breeding, we hypothesized that the stable carbon (δ13 C) and nitrogen (δ15 N) isotope values of individual amino acids (AAs) in endogenous stores (e.g. muscle) and in egg yolk and albumen reflect the nutrient sourcing that distinguishes capital versus income breeding. Unlike other methods, this approach does not require untested assumptions or diet sampling. We found that over half of essential AAs had δ13 C values that did not differ between muscle and yolk or albumen, suggesting that most of these AAs were directly routed from muscle into eggs. In contrast, almost all non-essential AAs differed in δ13 C values between muscle and yolk or between muscle and albumen, suggesting de novo synthesis. Over half of AAs that have labile nitrogen atoms (i.e. 'trophic' AA) had higher δ15 N values in yolk and albumen than in muscle, suggesting that they were transaminated during their routing into egg tissue. This effect was smaller for AAs with less labile nitrogen atoms (i.e. 'source' AA). Our results indicate that the δ15 N offset between trophic-source AAs (Δ15 Ntrophic-source ) may provide an index of the extent of capital breeding. The value of emperor penguin Δ15 NPro-Phe was higher in yolk and albumen than in muscle, reflecting the mobilization of endogenous stores; in comparison, the value of Δ15 NPro-Phe was similar across muscle and egg tissue in previously published data for income-breeding herring gulls Larus argentatus smithsonianus. Our results provide a quantitative basis for using AA δ13 C and δ15 N, and isotopic offsets among AAs (e.g. Δ15 NPro-Phe ), to explore the allocation of endogenous versus exogenous nutrients across the capital versus income spectrum of avian reproduction.

In Vivo Formation of HgSe Nanoparticles and Hg-Tetraselenolate Complex from Methylmercury in Seabirds-Implications for the Hg-Se Antagonism.

In vivo and in vitro evidence for detoxification of methylmercury (MeHg) as insoluble mercury selenide (HgSe) underlies the central paradigm that mercury exposure is not or little hazardous when tissue Se is in molar excess (Se:Hg > 1). However, this hypothesis overlooks the binding of Hg to selenoproteins, which lowers the amount of bioavailable Se that acts as a detoxification reservoir for MeHg, thereby underestimating the toxicity of mercury. This question was addressed by determining the chemical forms of Hg in various tissues of giant petrels Macronectes spp. using a combination of high energy-resolution X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopy, and transmission electron microscopy coupled to elemental mapping. Three main Hg species were identified, a MeHg-cysteinate complex, a four-coordinate selenocysteinate complex (Hg(Sec)4), and a HgSe precipitate, together with a minor dicysteinate complex Hg(Cys)2. The amount of HgSe decreases in the order liver > kidneys > brain = muscle, and the amount of Hg(Sec)4 in the order muscle > kidneys > brain > liver. On the basis of biochemical considerations and structural modeling, we hypothesize that Hg(Sec)4 is bound to the carboxy-terminus domain of selenoprotein P (SelP) which contains 12 Sec residues. Structural flexibility allows SelP to form multinuclear Hgx(Se,Sec)y complexes, which can be biomineralized to HgSe by protein self-assembly. Because Hg(Sec)4 has a Se:Hg molar ratio of 4:1, this species severely depletes the stock of bioavailable Se for selenoprotein synthesis and activity to one µg Se/g dry wet in the muscle of several birds. This concentration is still relatively high because selenium is naturally abundant in seawater, therefore it probably does not fall below the metabolic need for essential selenium. However, this study shows that this may not be the case for terrestrial animals, and that muscle may be the first tissue potentially injured by Hg toxicity.

Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science.

A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a stepwise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec)4) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ202Hg values for MeHg (2.69 ± 0.04‰), Hg(Sec)4 (-1.37 ± 0.06‰), and HgSe (0.18 ± 0.02‰) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ202Hg between MeHg and Hg(Sec)4 (-4.1 ± 0.1‰) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg → Hg(Sec)4 demethylation reaction. Surprisingly, Hg(Sec)4 and HgSe differed isotopically in δ202Hg (+1.6 ± 0.1‰) and mass-independent anomalies (i.e., changes in Δ199Hg of ≤0.3‰), consistent with equilibrium isotope effects of mass-dependent and nuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ202Hg values across tissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife.

Demethylation of Methylmercury in Bird, Fish, and Earthworm.

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate [Hg(Sec)4] complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy (HR-XANES) and chromatography-inductively coupled plasma mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.