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.

Vulnerability of the North Water ecosystem to climate change.

High Arctic ecosystems and Indigenous livelihoods are tightly linked and exposed to climate change, yet assessing their sensitivity requires a long-term perspective. Here, we assess the vulnerability of the North Water polynya, a unique seaice ecosystem that sustains the world's northernmost Inuit communities and several keystone Arctic species. We reconstruct mid-to-late Holocene changes in sea ice, marine primary production, and little auk colony dynamics through multi-proxy analysis of marine and lake sediment cores. Our results suggest a productive ecosystem by 4400-4200 cal yrs b2k coincident with the arrival of the first humans in Greenland. Climate forcing during the late Holocene, leading to periods of polynya instability and marine productivity decline, is strikingly coeval with the human abandonment of Greenland from c. 2200-1200 cal yrs b2k. Our long-term perspective highlights the future decline of the North Water ecosystem, due to climate warming and changing sea-ice conditions, as an important climate change risk.

Holocene polynya dynamics and their interaction with oceanic heat transport in northernmost Baffin Bay.

Baffin Bay hosts the largest and most productive of the Arctic polynyas: the North Water (NOW). Despite its significance and active role in water mass formation, the history of the NOW beyond the observational era remains poorly known. We reconcile the previously unassessed relationship between long-term NOW dynamics and ocean conditions by applying a multiproxy approach to two marine sediment cores from the region that, together, span the Holocene. Declining influence of Atlantic Water in the NOW is coeval with regional records that indicate the inception of a strong and recurrent polynya from ~ 4400 yrs BP, in line with Neoglacial cooling. During warmer Holocene intervals such as the Roman Warm Period, a weaker NOW is evident, and its reduced capacity to influence bottom ocean conditions facilitated northward penetration of Atlantic Water. Future warming in the Arctic may have negative consequences for this vital biological oasis, with the potential knock-on effect of warm water penetration further north and intensified melt of the marine-terminating glaciers that flank the coast of northwest Greenland.

Learning from the past: Impact of the Arctic Oscillation on sea ice and marine productivity off northwest Greenland over the last 9,000 years.

Climate warming is rapidly reshaping the Arctic cryosphere and ocean conditions, with consequences for sea ice and pelagic productivity patterns affecting the entire marine food web. To predict how ongoing changes will impact Arctic marine ecosystems, concerted effort from various disciplines is required. Here, we contribute multi-decadal reconstructions of changes in diatom production and sea-ice conditions in relation to Holocene climate and ocean conditions off northwest Greenland. Our multiproxy study includes diatoms, sea-ice biomarkers (IP25 and HBI III) and geochemical tracers (TOC [total organic carbon], TOC:TN [total nitrogen], δ13 C, δ15 N) from a sediment core record spanning the last c. 9,000 years. Our results suggest that the balance between the outflow of polar water from the Arctic, and input of Atlantic water from the Irminger Current into the West Greenland Current is a key factor in controlling sea-ice conditions, and both diatom phenology and production in northeastern Baffin Bay. Our proxy record notably shows that changes in sea-surface conditions initially forced by Neoglacial cooling were dynamically amplified by the shift in the dominant phase of the Arctic Oscillation (AO) mode that occurred at c. 3,000 yr BP, and caused drastic changes in community composition and a decline in diatom production at the study site. In the future, with projected dominant-positive AO conditions favored by Arctic warming, increased water column stratification may counteract the positive effect of a longer open-water growth season and negatively impact diatom production.

Arctic seabirds and shrinking sea ice: egg analyses reveal the importance of ice-derived resources.

In the Arctic, sea-ice plays a central role in the functioning of marine food webs and its rapid shrinking has large effects on the biota. It is thus crucial to assess the importance of sea-ice and ice-derived resources to Arctic marine species. Here, we used a multi-biomarker approach combining Highly Branched Isoprenoids (HBIs) with δ13C and δ15N to evaluate how much Arctic seabirds rely on sea-ice derived resources during the pre-laying period, and if changes in sea-ice extent and duration affect their investment in reproduction. Eggs of thick-billed murres (Uria lomvia) and northern fulmars (Fulmarus glacialis) were collected in the Canadian Arctic during four years of highly contrasting ice conditions, and analysed for HBIs, isotopic (carbon and nitrogen) and energetic composition. Murres heavily relied on ice-associated prey, and sea-ice was beneficial for this species which produced larger and more energy-dense eggs during icier years. In contrast, fulmars did not exhibit any clear association with sympagic communities and were not impacted by changes in sea ice. Murres, like other species more constrained in their response to sea-ice variations, therefore appear more sensitive to changes and may become the losers of future climate shifts in the Arctic, unlike more resilient species such as fulmars.

Ocean temperature impact on ice shelf extent in the eastern Antarctic Peninsula.

The recent thinning and retreat of Antarctic ice shelves has been attributed to both atmosphere and ocean warming. However, the lack of continuous, multi-year direct observations as well as limitations of climate and ice shelf models prevent a precise assessment on how the ocean forcing affects the fluctuations of a grounded and floating ice cap. Here we show that a +0.3-1.5 °C increase in subsurface ocean temperature (50-400 m) in the northeastern Antarctic Peninsula has driven to major collapse and recession of the regional ice shelf during both the instrumental period and the last 9000 years. Our projections following the representative concentration pathway 8.5 emission scenario from the Fifth Assessment Report of the Intergovernmental Panel on Climate Change reveal a +0.3 °C subsurface ocean temperature warming within the coming decades that will undoubtedly accelerate ice shelf melting, including the southernmost sector of the eastern Antarctic Peninsula.

Isoprenoid biosynthesis in the diatom Haslea ostrearia.

Diatoms are eukaryotic, unicellular algae that are responsible for c. 20% of the Earth's primary production. Their dominance and success in contemporary oceans have prompted investigations on their distinctive metabolism and physiology. One metabolic pathway that remains largely unexplored in diatoms is isoprenoid biosynthesis, which is responsible for the production of numerous molecules with unique features. We selected the diatom species Haslea ostrearia because of its characteristic isoprenoid content and carried out a comprehensive transcriptomic analysis and functional characterization of the genes identified. We functionally characterized one farnesyl diphosphate synthase, two geranylgeranyl diphosphate synthases, one short-chain polyprenyl synthase, one bifunctional isopentenyl diphosphate isomerase - squalene synthase, and one phytoene synthase. We inferred the phylogenetic origin of these genes and used a combination of functional analysis and subcellular localization predictions to propose their physiological roles. Our results provide insight into isoprenoid biosynthesis in H. ostrearia and propose a model of the central steps of the pathway. This model will facilitate the study of metabolic pathways of important isoprenoids in diatoms, including carotenoids, sterols and highly branched isoprenoids.

Sea ice and primary production proxies in surface sediments from a High Arctic Greenland fjord: Spatial distribution and implications for palaeoenvironmental studies.

In order to establish a baseline for proxy-based reconstructions for the Young Sound-Tyrolerfjord system (Northeast Greenland), we analysed the spatial distribution of primary production and sea ice proxies in surface sediments from the fjord, against monitoring data from the Greenland Ecosystem Monitoring Programme. Clear spatial gradients in organic carbon and biogenic silica contents reflected marine influence, nutrient availability and river-induced turbidity, in good agreement with in situ measurements. The sea ice proxy IP25 was detected at all sites but at low concentrations, indicating that IP25 records from fjords need to be carefully considered and not directly compared to marine settings. The sea ice-associated biomarker HBI III revealed an open-water signature, with highest concentrations near the mid-July ice edge. This proxy evaluation is an important step towards reliable palaeoenvironmental reconstructions that will, ultimately, contribute to better predictions for this High Arctic ecosystem in a warming climate.

Trace elements in Antarctic fish species and the influence of foraging habitats and dietary habits on mercury levels.

This study aims at describing and interpreting concentration profiles of trace elements in seven Antarctic fish species (N=132 specimens) off Adélie Land. Ichthyofauna plays a key role in the Antarctic ecosystem, as they occupy various ecological niches, including cryopelagic (ice-associated), pelagic, and benthic habitats. Firstly, trace element levels in the studied specimens were similar to those previously observed in fish from the Southern Ocean. Apart from manganese and zinc, concentrations of arsenic, cadmium, copper, iron, mercury (Hg), nickel, selenium and silver differed among fish species. Muscle δ(13)C and δ(15)N values were determined to investigate whether the fish foraging habitats and dietary habits could explain Hg levels. Species and foraging habitat (δ(13)C) were strong predictors for variations of Hg concentrations in muscle tissues. The highest Hg contamination was found in shallow benthic fish compared to cryopelagic and pelagic fish. This pattern was likely due to the methylation of Hg in the coastal sediment and the photodemethylation by ultraviolet radiation in surface waters.

Ocean lead at the termination of the Younger Dryas cold spell.

The Younger Dryas (YD) cold interval is one of the most abrupt climate events of Earth's recent history. The origin of this rapid, severe cooling episode is still widely debated, but it was probably triggered by a large freshwater influx to the North Atlantic resulting in disruption of the Atlantic Meridional Overturning Circulation. The YD termination, despite having been even more abrupt than the onset has, however, received significantly less attention. Here using multi-proxy data from a high-resolution marine sediment record, we present evidence for a gradual decrease of the Labrador Current influence, northward migration of the Gulf Stream oceanic front and a rapid decline of sea-ice cover at the YD termination. Our data indicate a stepwise sequence of events with changes in ocean circulation clearly preceding those in atmospheric conditions, in contrast to the hitherto commonly assumed single-event rapid climatic shift at the YD-Holocene transition.

Diatom-specific highly branched isoprenoids as biomarkers in Antarctic consumers.

The structure, functioning and dynamics of polar marine ecosystems are strongly influenced by the extent of sea ice. Ice algae and pelagic phytoplankton represent the primary sources of nutrition for higher trophic-level organisms in seasonally ice-covered areas, but their relative contributions to polar marine consumers remain largely unexplored. Here, we investigated the potential of diatom-specific lipid markers and highly branched isoprenoids (HBIs) for estimating the importance of these two carbon pools in an Antarctic pelagic ecosystem. Using GC-MS analysis, we studied HBI biomarkers in key marine species over three years in Adélie Land, Antarctica: euphausiids (ice krill Euphausia crystallorophias and Antarctic krill E. superba), fish (bald notothens Pagothenia borchgrevinki and Antarctic silverfish Pleuragramma antarcticum) and seabirds (Adélie penguins Pygoscelis adeliae, snow petrels Pagodroma nivea and cape petrels Daption capense). This study provides the first evidence of the incorporation of HBI lipids in Antarctic pelagic consumers. Specifically, a di-unsaturated HBI (diene) of sea ice origin was more abundant in ice-associated species than in pelagic species, whereas a tri-unsaturated HBI (triene) of phytoplanktonic origin was more abundant in pelagic species than in ice-associated species. Moreover, the relative abundances of diene and triene in seabird tissues and eggs were higher during a year of good sea ice conditions than in a year of poor ice conditions. In turn, the higher contribution of ice algal derived organic matter to the diet of seabirds was related to earlier breeding and higher breeding success. HBI biomarkers are a promising tool for estimating the contribution of organic matter derived from ice algae in pelagic consumers from Antarctica.

Isoprenoid biosynthesis in the diatoms Rhizosolenia setigera (Brightwell) and Haslea ostrearia (Simonsen).

Isoprenoid biosynthesis in the widespread diatomaceous algae, Rhizosolenia setigera (Brightwell) and Haslea ostrearia (Simonsen), results not only in the production of diterpenoids, triterpenoids, and sterols but, unusually for diatoms, also in the production of sesterterpenoids. By using 13C and 2H isotopic labeling techniques followed by NMR and mass spectrometry, specific inhibition of mevalonate (MVA) and methylerythritol (MEP) pathways, and comparison with the natural 13C/12C isotope ratios of the lipids, the different biosynthetic pathways of the sesterterpenes and other isoprenoids have now been determined. Surprisingly, whereas the sesterterpenes (Delta(7(20))-haslenes) in R. setigera were made by the MVA pathway, as were the related triterpenoid rhizenes and desmosterol, in H. ostrearia the structurally similar Delta(6(17))-haslenes and the major sterol, 24-ethylcholest-5-en-3beta-ol, were instead biosynthesized by the MEP route. Phytol was biosynthesized in both diatoms by the MEP route. Subfractionation of R. setigera cells revealed that although phytol was located in the chloroplasts, the haslenes, rhizenes, and sterols were present in the cytoplasm. The observations described here for R. setigera and H. ostrearia show that terpenoid biosynthesis in diatoms is species-dependent and cannot simply be grouped according to structural type. Triterpenes appear to be made by the MVA route as in higher plants, whereas sesterterpenes and sterols can be made by either the MVA or MEP routes. In neither organism were the isoprenoids biosynthesized by leucine metabolism. Sesterterpene and triterpene biosynthesis in diatoms has not been investigated previously.

The rise of the rhizosolenid diatoms.

The 18S ribosomal DNA molecular phylogeny and lipid composition of over 120 marine diatoms showed that the capability to biosynthesize highly branched isoprenoid (HBI) alkenes is restricted to two specific phylogenetic clusters, which independently evolved in centric and pennate diatoms. The molecular record of C25 HBI chemical fossils in a large suite of well-dated marine sediments and petroleum revealed that the older cluster, composed of rhizosolenid diatoms, evolved 91.5 +/- 1.5 million years ago (Upper Turonian), enabling an accurate dating of the pace of diatom evolution that is unprecedented. The rapid rise of the rhizosolenid diatoms probably resulted from a major reorganization of the nutrient budget in the mid-Cretaceous oceans, triggered by plate tectonics.

Effects of auxosporulation on distributions of C(25) and C(30) isoprenoid alkenes in Rhizosolenia setigera.

The effect of life cycle on the distributions of C(25) and C(30) highly branched isoprenoid (HBI) alkene lipids has been investigated for the marine diatom Rhizosolenia setigera. The concentrations of the C(30) compounds are largely independent of the cell volume, though the ratios of the individual isomers possessing five and six double bonds show a dependence on the position of the cell during its life cycle, especially during auxosporulation. In contrast to the C(30) pseudo-homologues, the C(25) isomers are not always detected in cultures of R. setigera. The biosynthesis of the C(25) HBIs would appear to result from the onset of auxosporulation, with further changes to their distributions taking place after this phase, including the formation of more unsaturated isomers. The results of this investigation may be used in part to explain the large variations in these lipids reported previously.