Spatial distribution of selenium-mercury in Arctic seabirds.

Mercury (Hg) is a metallic trace element toxic for humans and wildlife that can originate from natural and anthropic sources. Hg spatial gradients have been found in seabirds from the Arctic and other oceans, suggesting contrasting toxicity risks across regions. Selenium (Se) plays a protective role against Hg toxicity, but its spatial distribution has been much less investigated than that of Hg. From 2015 to 2017, we measured spatial co-exposure of Hg and Se in blood samples of two seabird species, the Brünnich's guillemot (Uria lomvia) and the black-legged kittiwake (Rissa tridactyla) from 17 colonies in the Arctic and subarctic regions, and we calculated their molar ratios (Se:Hg), as a measure of Hg sequestration by Se and, therefore, of Hg exposure risk. We also evaluated concentration differences between species and ocean basins (Pacific-Arctic and Atlantic-Arctic), and examined the influence of trophic ecology on Hg and Se concentrations using nitrogen and carbon stable isotopes. In the Atlantic-Arctic ocean, we found a negative west-to-east gradient of Hg and Se for guillemots, and a positive west-to-east gradient of Se for kittiwakes, suggesting that these species are better protected from Hg toxicity in the European Arctic. Differences in Se gradients between species suggest that they do not follow environmental Se spatial variations. This, together with the absence of a general pattern for isotopes influence on trace element concentrations, could be due to foraging ecology differences between species. In both oceans, the two species showed similar Hg concentrations, but guillemots showed lower Se concentrations and Se:Hg than kittiwakes, suggesting a higher Hg toxicity risk in guillemots. Within species, neither Hg, nor Se or Se:Hg differed between both oceans. Our study highlights the importance of considering Se together with Hg, along with different species and regions, when evaluating Hg toxic effects on marine predators in international monitoring programs.

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.

The consumption of ice-derived resources is associated with higher mercury contamination in an Arctic seabird.

Sea ice plays a fundamental role in Arctic marine environments, by driving primary productivity and sustaining ice-associated ecosystems. Simultaneously, sea ice influences the contamination of Arctic marine organisms, by modifying contaminant cycles or their bioavailability. Changes in sea ice conditions could therefore profoundly impact the functioning of Arctic marine food webs and their contamination. Top predators such as seabirds, which are subject to bioaccumulation and biomagnification of contaminants, are particularly exposed. In this context, the present study aims to investigate the influence of sea ice and of the use of ice-derived resources on the contamination of seabirds by mercury (Hg). To this end, eggs of thick-billed murres (Brünnich's guillemots, Uria lomvia; n = 60) were collected on Prince Leopold Island (Canadian High Arctic) during four years of varying ice conditions (2010-2013). Trophic tracers (i.e., Highly Branched Isoprenoids, HBIs - an indicator of the use of ice-derived resources; carbon and nitrogen stable isotopes - indicators of foraging habitats and trophic status), as well as total Hg concentrations were quantified. Results showed that feeding on ice-derived resources (as indicated by HBI concentrations) was positively correlated to sea ice cover, and both positively influenced Hg concentrations in murre eggs. However, when testing for the best predictor with model selection, sea ice concentration only drove Hg contamination in murres. This work provides new insights into the role of sea ice and ice-derived resources in the contamination by Hg of Arctic wildlife. Further research is now needed to better understand the relationship between sea ice and Hg contamination in Arctic biota and its underlying mechanisms, but also to identify Hg sources in rapidly changing environmental conditions in the Arctic.

Isotopic and biochemical trophic markers reveal the complexity of interactions at the base of pelagic food webs (Mediterranean sea).

To gain insight into the impact of bottom-up changes in the plankton community on planktivorous fish in the context of the decline of small pelagic fisheries in the Northwestern Mediterranean Sea, we have conducted an extensive year-long study. The investigation combined biochemical analyses (proteins, carbohydrates, and lipids) with C and N stable isotope analyses (SIA) to simultaneously study phytoplankton, zooplankton, and eight planktivorous fish species (Engraulis encrasicolus, Sardina pilchardus, Sardinella aurita, Sprattus sprattus, Cepola macrophthalma, Chromis chromis, Boops boops, and Spicara maena). This study is the first to analyze both stable isotope and biochemical compositions in coastal particulate organic matter (POM) size classes (0.7-2.7 µm, 2.7-20 µm, and 20-200 µm), zooplankton size classes (200-300 µm, 300-500 µm, 500-1000 µm, 1000-2000 µm, and >2000 µm), and taxonomic groups. We demonstrated that: (1) POM stable isotope compositions varied based on its spatial origin, the taxonomic composition of its biota, and its biochemical content; (2) δ15N values increased with zooplankton size classes and groups, indicating different trophic levels; (3) Phytoplankton exhibited a lipid-rich composition (∼55%), while zooplankton and fish muscles were protein-rich (∼61% and ∼66%, respectively). Bayesian stable isotope mixing models revealed that, on average: (1) POM from oceanic waters contributed the most to the POM in the bay (>51%), with a dominance of pico-POM (∼43%); (2) The 200-1000 µm zooplankton primarily consumed nano-POM, the 1000-2000 µm zooplankton mostly consumed micro-POM (∼64%), and the >2000 µm zooplankton also mostly consumed micro-POM; (3) Mesozooplankton (200-2000 µm) constituted the main portion (∼42%) of the diet for planktivorous fish species, while macrozooplankton organisms (>2000 µm) were the primary food resource (∼43%) for both B. boops and S. sprattus. Our study underscores the complexity of the pelagic food web and highlights the bottom-up transfer of organic matter from the smallest phytoplankton size fractions to planktivorous fish.

Spatial variations of biochemical content and stable isotope ratios of size-fractionated plankton in the Mediterranean Sea (MERITE-HIPPOCAMPE campaign).

Plankton represents the main source of carbon in marine ecosystems and is consequently an important gateway for contaminants into the marine food webs. During the MERITE- HIPPOCAMPE campaign in the Mediterranean Sea (April-May 2019), plankton was sampled from pumping and net tows at 10 stations from the French coast to the Gulf of Gabès (Tunisia) to obtain different size fractions in contrasted regions. This study combines various approaches, including biochemical analyses, analyses of stable isotope ratios (δ13C, δ15N), cytometry analyses and mixing models (MixSiar) on size-fractions of phyto- and zooplankton from 0.7 to >2000 µm. Pico- and nanoplankton represented a large energetic resource at the base of pelagic food webs. Proteins, lipids, and stable isotope ratios increased with size in zooplankton and were higher than in phytoplankton. Stable isotope ratios suggest different sources of carbon and nutrients at the base of the planktonic food webs depending on the coast and the offshore area. In addition, a link between productivity and trophic pathways was shown, with high trophic levels and low zooplankton biomass recorded in the offshore area. The results of our study highlight spatial variations of the trophic structure within the plankton size-fractions and will contribute to assess the role of the plankton as a biological pump of contaminants.

High inter-species variability in elemental composition of the twilight zone fauna varies implications for predators and exploitation by humans.

While the importance of oceanic micronektonic species in biogeochemical cycles and in the transfer of matter in food webs is globally recognized, specific knowledge on elemental concentrations and their variability within this community is still poorly documented. Here, we report for the first time in the Bay of Biscay, North-East Atlantic, the body composition in various biological parameters and chemical elements of a meso-to bathypelagic micronektonic community. Stable carbon and nitrogen isotope compositions (δ13C, δ15N), C:N ratios, energy density, as well as the concentrations in 6 macro-minerals and 13 trace elements including essential (micro-nutrients) and non-essential elements (undesirables, with no know biological function) were measured in whole organisms of 4 crustacean and 11 fish species caught simultaneously around 800 m depth. The results showed a low variability of δ13C values, confirming that all studied species share the same habitat. On the contrary, large differences were observed among species for several elements. Trace elements showed the greatest variability (i.e. larger range of values), especially silver (Ag), arsenic (As), cadmium (Cd), cobalt and vanadium. Significant differences were also revealed among taxa for Ag, As, Cd, copper and strontium concentrations (with crustaceans > fish), as well as for δ15N values and phosphorus concentrations (with fish > crustaceans). Although concentrations varied greatly among species, they could be grouped according to their energy density and composition in 19 chemical elements, through hierarchical clustering analysis. Six functional groups of species have been thus identified, reflecting contrasted nutritional benefit and/or exposure to undesirables for predators feeding on this deep pelagic community. Finally, the concentrations measured for the potentially toxic trace elements (undesirables) exceeded the existing European thresholds for Cd and to a lesser extent mercury (Hg), which point out potential risks in the perspective of a future exploitation of these deep living resources by humans.

Trophic niche overlap between sympatric harbour seals (Phoca vitulina) and grey seals (Halichoerus grypus) at the southern limit of their European range (Eastern English Channel).

Sympatric harbour (Phoca vitulina) and grey seals (Halichoerus grypus) are increasingly considered potential competitors, especially since recent local declines in harbour seal numbers while grey seal numbers remained stable or increased at their European core distributions. A better understanding of the interactions between these species is critical for conservation efforts. This study aimed to identify the trophic niche overlap between harbour and grey seals at the southern limit of their European range, in the Baie de Somme (BDS, Eastern English Channel, France), where numbers of resident harbour seals and visiting grey seals are increasing exponentially. Dietary overlap was identified from scat contents using hierarchical clustering. Isotopic niche overlap was quantified using δ13C and δ15N isotopic values from whiskers of 18 individuals, by estimating isotopic standard ellipses with a novel hierarchical model developed in a Bayesian framework to consider both intraindividual variability and interindividual variability. Foraging areas of these individuals were identified from telemetry data. The three independent approaches provided converging results, revealing a high trophic niche overlap due to consumption of benthic flatfish. Two diet clusters were dominated by either small or large benthic flatfish; these comprised 85.5% [CI95%: 80.3%-90.2%] of harbour seal scats and 46.8% [35.1%-58.4%] of grey seal scats. The narrower isotopic niche of harbour seals was nested within that of grey seals (58.2% [22.7%-100%] overlap). Grey seals with isotopic values similar to harbour seals foraged in coastal waters close to the BDS alike harbour seals did, suggesting the niche overlap may be due to individual grey seal strategies. Our findings therefore provide the basis for potential competition between both species (foraging on benthic flatfish close to the BDS). We suggest that a continued increase in seal numbers and/or a decrease in flatfish supply in this area could cause/amplify competitive interactions and have deleterious effects on harbour seal colonies.

Using GPS tracking and stable multi-isotopes for estimating habitat use and winter range in Palearctic ospreys.

We used both satellite tracking and carbon, nitrogen and sulphur stable isotopic analysis (SIA) to infer wintering ecology and habitat use of the Corsican osprey Pandion haliaetus population. A control sample of feathers from 75 individuals was collected within the osprey's northern hemisphere breeding range, to assess the SIA variability across habitat types. An experimental set of SIA on feathers of 18 Corsican adults was examined to infer wintering ground locations and habitat types used during the non-breeding period. We calibrated the SIA using GPS/GSM tracks of 12 Mediterranean adults' movements as wintering site references. We found 50% of individuals were resident and the other half migrated. Ospreys spent the winter at temperate latitudes and showed a high plasticity in habitat selection spread over the Mediterranean basin (marine bays, coastal lagoons/marshland, inland freshwater sites). Complementary to GPS tracking, SIA is, at a broad geographical scale, a reliable method to determine whether ospreys overwinter in a habitat different from that of their breeding area. This study proved that the integration of SIA and GPS/GSM tracking techniques was effective at overcoming the intrinsic limits of each method and achieving greater information for basic ecological studies of migratory birds in aquatic environments.

Mercury in blue shark (Prionace glauca) and shortfin mako (Isurus oxyrinchus) from north-eastern Atlantic: Implication for fishery management.

Pelagic sharks (blue shark Prionace glauca and shortfin mako Isurus oxyrinchus) caught by long-line Spanish and Portuguese fleets in the NE Atlantic, were sampled at Vigo fish market (Spain) for total mercury (Hg) analysis. Hg concentration in white muscle increased with size and weight in both species, but at a higher rate in shortfin mako than in the blue shark. No difference was found with sex, year and season. Spatial variation was observed in the blue shark with higher Hg values in the North of the Azorean archipelago, but not in the shortfin mako. These high-level predators are particularly susceptible to bioaccumulate contaminants (Hg) in their tissues (muscle). However, a significant positive relationship between Hg concentration and trophic level (δ15N) of individuals was observed only in the shortfin mako. Most sharks landed were juveniles which presented Hg concentration lower than the maximum limit allowed by the European Union (1mgkg-1 wet weight) for marketing. However, concentrations above this threshold were most recorded in blue sharks larger than 250cm total length (TL) and in shortfin makos larger than 190cm TL, raising the question of the commercialization of large-sized individuals.

Does reef structure affect oyster food resources? A stable isotope assessment.

As ecosystem engineers, oysters create and maintain structured habitat and can influence trophodynamics and benthic-pelagic coupling in the surrounding landscape. The physical reef structure and associated biotic parameters can affect the availability of food resources for oysters. Oysters and potential composite food sources - suspended particulate organic matter (SPOM) and surface sediment organic matter (SSOM) - were assessed using a dual stable isotope (δ13C, δ15N) approach at three reef types (natural, restored, and unconsolidated) seasonally for two years to determine if changes in physical and/or biotic parameters affected the relative availability and/or use of food resources by oysters. SPOM was more depleted in 13C (-24.2 ± 0.6‰, mean ± SD) than SSOM (-21.2 ± 0.8‰). SPOM composition is likely dominated by autochthonous phytoplankton production, while SSOM includes trapped phytoplankton and benthic microalgae. SSOM was used by oysters in increasing proportions relative to SPOM over time at all reef types. This temporal trend is likely due to increased oyster biomass over time, promoting enhanced microphytobenthos growth through feedback effects related to oyster biodeposits. Structural differences between reef types observed in this study had no effect on food resource availability and use by oysters, indicating strong bentho-pelagic coupling likely due to shallow depths as well as strong and consistent winds. This study provides insights for restoration of oyster reefs as it highlights that food resources used by oysters remain similar among reef types despite changes in abiotic and biotic parameters among habitats and over time.

Seasonal Variation of Harbor Seal's Diet from the Wadden Sea in Relation to Prey Availability.

The Wadden Sea has an important role for marine mammals in terms of resting, nursing and foraging. Harbor seal is the most abundant marine mammal species in this area. The use of the food resources of the Wadden Sea by seals is not clear, and previous studies showed that this species can travel kilometers away from their haul-outs to forage in the North Sea. In this study, we analyzed the stable isotopes of vibrissae from 23 dead harbor seals found on the island of Sylt to investigate their diet. The predator´s carbon and nitrogen isotope compositions were compared to the compositions of different potential prey items from the Sylt-Rømø Bight and from the North Sea in order to study seasonal pattern in the diet and in the foraging location. In parallel, seasonal variation of abundance and biomass of the potential prey items from the Sylt-Rømø Bight were studied and compare to their contribution to the seal´s diet. The results revealed a change in the seal´s diet from pelagic sources in spring to a benthic based diet in summer, and an increasing use of the North Sea resources in fall and winter in accordance with the seasonal variation of the availability of prey in the Sylt-Rømø Bight.

Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰).

Methods of lipid-normalization for multi-tissue stable isotope analyses in tropical tuna.

RATIONALE: The bias associated with lipid contents in fish tissues is a recalcitrant topic for trophic studies using stable isotopes. Lipids are depleted in the heavy carbon isotope ((13)C) and the lipid content varies considerably among species, tissues and in both time and space. We have applied and assessed different correction methods for tropical tuna tissues. METHODS: We tested two types of normalization methods to deal with variable lipid content in liver, gonads, and white and red muscles of yellowfin, bigeye and skipjack tuna: a chemical extraction using dichloromethane and a mathematical correction based on three modeling approaches (linear, non-linear and mass balance models). We measured isotopic ratios of bulk and lipid-free tissues and assessed the predictive ability of the correction models with the lipid-free measurements. The parameters of the models were estimated from our dataset and from results from published studies on other species. RESULTS: Comparison between bulk, lipid-free and lipid-corrected isotopic ratios demonstrated that (1) chemical extraction using dichloromethane did not affect δ(15)N values; (2) the change in δ(13)C values after extraction was tissue-specific; (3) lipid-normalization models using published parameter estimates failed to predict lipid-corrected δ(13)C values; and (4) linear and non-linear models using parameters estimated for each tissue from our dataset provided accurate δ(13)C predictions for all tissues, and mass balance model for white muscle only. CONCLUSIONS: Models using published estimates for parameters from other species cannot be used. Based on a range of lipid content that do not exceed 45%, we recommend the linear model to correct the bulk δ(13)C values in the investigated tissues but the parameters have to be estimated from a proportion of the original data for which chemical extraction is required and the isotopic values of bulk and lipid-free tissues are measured.

Major Sources of Organic Matter in a Complex Coral Reef Lagoon: Identification from Isotopic Signatures (δ13C and δ15N).

A wide investigation was conducted into the main organic matter (OM) sources supporting coral reef trophic networks in the lagoon of New Caledonia. Sampling included different reef locations (fringing, intermediate and barrier reef), different associated ecosystems (mangroves and seagrass beds) and rivers. In total, 30 taxa of macrophytes, plus pools of particulate and sedimentary OM (POM and SOM) were sampled. Isotopic signatures (C and N) of each OM sources was characterized and the composition of OM pools assessed. In addition, spatial and seasonal variations of reef OM sources were examined. Mangroves isotopic signatures were the most C-depleted (-30.17 ± 0.41 ‰) and seagrass signatures were the most C-enriched (-4.36 ± 0.72 ‰). Trichodesmium spp. had the most N-depleted signatures (-0.14 ± 0.03 ‰) whereas mangroves had the most N-enriched signatures (6.47 ± 0.41 ‰). The composition of POM and SOM varied along a coast-to-barrier reef gradient. River POM and marine POM contributed equally to coastal POM, whereas marine POM represented 90% of the POM on barrier reefs, compared to 10% river POM. The relative importance of river POM, marine POM and mangroves to the SOM pool decreased from fringing to barrier reefs. Conversely, the relative importance of seagrass, Trichodesmium spp. and macroalgae increased along this gradient. Overall, spatial fluctuations in POM and SOM were much greater than in primary producers. Seasonal fluctuations were low for all OM sources. Our results demonstrated that a large variety of OM sources sustain coral reefs, varying in their origin, composition and role and suggest that δ13C was a more useful fingerprint than δ15N in this endeavour. This study also suggested substantial OM exchanges and trophic connections between coral reefs and surrounding ecosystems. Finally, the importance of accounting for environmental characteristics at small temporal and spatial scales before drawing general patterns is highlighted.