Guillaume Massé

Identification of a C25 highly branched isoprenoid (HBI) diene in Antarctic sediments, Antarctic sea-ice diatoms and cultured diatoms

Abstract A highly branched isoprenoid (HBI) diene found in Antarctic sea-ice diatoms and surface layer (0–2 cm) sediments from Antarctica is identified as 2,10,14-trimethyl-6-methylene-7-(3′-methylpent-1-enyl)pentadecane. The identification was made by comparison of GC–MS mass spectra and retention indices on both polar and apolar GC stationary phases with those of the diene authenticated by NMR after isolation from a laboratory culture of the diatom, Haslea ostrearia .

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.

Persistent organic pollutants in benthic and pelagic organisms off Adélie Land, Antarctica

The concentrations of polychlorinated biphenyls (PCB), hexachlorobenzene (HCB), pentachlorobenzene (PeCB) and polybrominated diphenylethers (PBDE) were described in benthic and pelagic species collected off Adélie Land, Antarctica. Strong differences were observed among species, with reduced PeCB and HCB levels in benthic species, and elevated PCB levels in the Antarctic yellowbelly rockcod, the Antarctic sea urchin and the snow petrel. Lower-chlorinated congeners were predominant in krill; penta-PCBs in benthic organisms; hexa- and hepta-PCBs in seabirds and cryopelagic fish. This segregation may result from sedimentation process, specific accumulation and excretion, and/or biotransformation processes. The presence of PBDEs in Antarctic coastal organisms may originate from atmospheric transport and partly from a contamination by local sources. Although POP levels in Antarctic marine organisms were substantially lower than in Arctic and temperate organisms, very little is known about their toxic effects on these cold-adapted species, with high degree of endemism.

Holocene climate variations in the western Antarctic Peninsula: evidence for sea ice extent predominantly controlled by changes in insolation and ENSO variability

The West Antarctic ice sheet is particularly sensitive to global warming and its evolution and impact on global climate over the next few decades remains difficult to predict. In this context, investigating past sea ice conditions around Antarctica is of primary importance. Here, we document changes in sea ice presence, upper water column temperatures (0-200 m) and primary productivity over the last 9000 yr BP (before present) in the western Antarctic Peninsula (WAP) margin from a sedimentary core collected in the Palmer Deep Basin. Employing a multi-proxy approach, based on the combination of two biomarkers proxies (highly branched isoprenoid (HBI) alkenes for sea ice and TEX86L for temperature) and micropaleontological data (diatom assemblages), we derived new Holocene records of sea ice conditions and upper water column temperatures. The early Holocene (9000-7000 yr BP) was characterized by a cooling phase with a short sea ice season. During the mid-Holocene (~7000-3800 yr BP), local climate evolved towards slightly colder conditions and a prominent extension of the sea ice season occurred, promoting a favorable environment for intensive diatom growth. The late Holocene (the last ~2100 yr) was characterized by warmer temperatures and increased sea ice presence, accompanied by reduced local primary productivity, likely in response to a shorter growing season compared to the early or mid-Holocene. The gradual increase in annual sea ice duration over the last 7000 yr might have been influenced by decreasing mean annual and spring insolation, despite increasing summer insolation. We postulate that, in addition to precessional changes in insolation, seasonal variability, via changes in the strength of the circumpolar Westerlies and upwelling activity, was further amplified by the increasing frequency/amplitude of the El Nino-Southern Oscillation (ENSO). However, between 3800 and 2100 yr BP, the lack of correlation between ENSO and climate variability in the WAP suggests that other climatic factors might have been more important in controlling WAP climate at this time.

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.

Configurations of polyunsaturated sesterterpenoids from the diatom, Haslea ostrearia.

The partial configurations of C25 isoprenoid alkenes isolated from the diatom Haslea ostrearia Gaillon (Simonsen) have been established. A combination of NMR spectroscopy studies of the alkenes with chiral shift reagents in conjunction with soluble silver beta-diketonate complexes and enantioselective gas chromatography of oxidation products of the alkenes was used. Unexpected differences in highly branched isoprenoid isomer configurations were observed between different laboratory cultures of the alga.

Autoxidative and Photooxidative Reactivity of Highly Branched Isoprenoid (HBI) Alkenes

Autoxidation of several mono-, di-, tri- and tetra-unsaturated highly branched isoprenoid (HBI) alkenes was induced in organic solvents using a radical initiator and enhancer, and their degradation rates were compared to those of classical phytoplanktonic lipids (mono-unsaturated fatty acids, sterols and chlorophyll phytyl side-chain). Autoxidation of two HBI trienes was also investigated in senescent and highly photodegraded diatom cells, collected in the Antarctic, using Fe2+ ions as radical inducers. Autoxidation rates of HBI alkenes were found to increase with the number of tri-substituted double bonds, as expected. Further, HBI trienes possessing one bis-allylic position (where hydrogen abstraction is highly favoured) were found to be particularly reactive towards autoxidation and degraded at similar rates compared to polyunsaturated fatty acids in diatom cells. By comparison of the autoxidation products of the most reactive tri-unsaturated HBI with the corresponding photooxidation products, some specific tracers of these two types of abiotic degradation processes were identified. The lack of reactivity of the mono-unsaturated HBI IP25 and a structurally similar di-unsaturated HBI towards autoxidative degradation supports the good preservation of these biomarkers in marine sediments.

Sea ice diatom contributions to Holocene nutrient utilization in East Antarctica

Combined high-resolution Holocene δ30Sidiat and δ13Cdiat paleorecords are presented from the Seasonal Ice Zone, East Antarctica. Both data sets reflect periods of increased nutrient utilization by diatoms during the Hypsithermal period (circa 7800 to 3500 calendar years (cal years) B.P.), coincident with a higher abundance of open water diatom species (Fragilariopsis kerguelensis), increased biogenic silica productivity (%BSi), and higher regional summer temperatures. The Neoglacial period (after circa 3500 cal years B.P.) is reflected by an increase in sea ice indicative species (Fragilariopsis curta and Fragilariopsis cylindrus, up to 50%) along with a decrease in %BSi and δ13Cdiat (< −18‰ to −23‰). However, over this period, δ30Sidiat data show an increasing trend, to some of the highest values in the Holocene record (average of +0.43‰). Competing hypotheses are discussed to account for the decoupling trend in utilization proxies including iron fertilization, species-dependent fractionation effects, and diatom habitats. Based on mass balance calculations, we highlight that diatom species derived from the semi-enclosed sea ice environment may have a confounding effect upon δ30Sidowncore compositions of the seasonal sea ice zone. A diatom composition, with approximately 28% of biogenic silica derived from the sea ice environment (diat-SI) can account for the increased average composition of δ30Sidiat during the Neoglacial. These data highlight the significant role sea ice diatoms can play with relation to their export in sediment records, which has implications on productivity reconstructions from the seasonal ice zone.

High turnover rates indicated by changes in the fixed N forms and their stable isotopes in Antarctic landfast sea ice

We report concentration and nitrogen and oxygen isotopic measurements of nitrate, total dissolved nitrogen, and particulate nitrogen from Antarctic landfast sea ice, covering almost the complete seasonal cycle of sea ice growth and decay (from April to November). When sea ice forms in autumn, ice algae growth depletes nitrate and accumulates organic N within the ice. Subsequent low biological activity in winter imposes minor variations in the partitioning of fixed N. In early spring, the coupling between nitrate assimilation and brine convection at the sea ice bottom traps a large amount of fixed N within sea ice, up to 20 times higher than in the underlying seawater. At this time, remineralization and nitrification also accelerate, yielding nitrate concentrations up to 5 times higher than in seawater. Nitrate δ15N and δ18O are both elevated, indicating a near-balance between nitrification and nitrate assimilation. These findings require high microbially mediated turnover rates for the large fixed N pools, including nitrate. When sea ice warms in the spring, ice algae grow through the full thickness of the ice. The warming stratifies the brine network, which limits the exchange with seawater, causing the once-elevated nitrate pool to be nearly completely depleted. The nitrate isotope data point to light limitation at the base of landfast ice as a central characteristic of the environment, affecting its N cycling (e.g., allowing for nitrification) and impacting algal physiology (e.g., as reflected in the N and O isotope effects of nitrate assimilation).

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

Abstract 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.