Massé G., Belt S., Crosta, X., Schmidt S., Snape, I., Thomas, D.N., Rowland S.J. (2011). Highly branched isoprenoids as proxies for variable sea ice conditions in the Southern Ocean. Antarct. Sci., .
Abstract: Concentrations of a highly branched isoprenoid (HBI) diene determined in over 200 sediment samples from the Arctic co-vary with those of an HBI monoene (IP25) shown previously to be a sedimentary sea ice proxy for the Arctic. The same diene, but not monoene IP25, occurred in nine sea ice samples collected from various locations around Antarctica. The diene has been reported previously in Antarctic sea ice diatoms and the 13C isotopic compositions of the diene determined in two Antarctic sea ice samples were also consistent with an origin from sea ice diatoms (δ13C -5.7 to -8.5‰). In contrast, HBIs found in two Antarctic phytoplankton samples did not include the diene but comprised a number of tri- to pentaenes. In sediment samples collected near Adélie Land, East Antarctica, both the diene and the tri- to pentaenes often co-occurred. 13C isotopic compositions of the tri- to pentaenes in three sediment samples ranged from -35 to -42‰ whereas that of the diene in a sediment sample was -18‰. We propose the presence of this isotopically 13C enriched HBI diene in Antarctic sediments to be a useful proxy indicator for contributions of organic matter derived from sea ice diatoms. A ratio of the concentrations of diene/trienes might reflect the relative contributions of sea ice to phytoplanktonic inputs of organic matter to Antarctic sediments.
Programme: 1010
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Jean-François Rontani, Lukas Smik, Simon T. Belt, Frédéric Vaultier, Linda Armbrecht, Amy Leventer, Leanne K. Armand. (2019). Abiotic degradation of highly branched isoprenoid alkenes and other lipids in the water column off East Antarctica (Vol. 210).
Abstract: In some previous studies, the ratio between a di-unsaturated highly branched isoprenoid (HBI) lipid termed IPSO25 and a structurally related tri-unsaturated counterpart (HBI III) (viz. IPSO25/HBI III) has been used as a proxy measure of variable sea ice cover in the Antarctic owing to their production by certain sea ice algae and open water diatoms, respectively. To investigate this further, we quantified selected lipids and their photo- and autoxidation products in samples of suspended particulate matter (SPM) collected at different water depths in the polynya region west of the Dalton Iceberg Tongue (East Antarctica). The results obtained confirm the high efficiency of photo- and autoxidation processes in diatoms from the region. The systematic increase of the ratio IPSO25/HBI III with water depth in the current samples appeared to be dependent on the sampling site and was due to both (i) a relatively higher contribution of ice algae to the deeper samples resulting from their increased aggregation and therefore higher sinking rate, or (ii) a stronger abiotic degradation of HBI III during settling through the water column. Analyses of samples taken from the water-sediment interface and some underlying near-surface sediments revealed a further increase of the ratio IPSO25/HBI III, indicative of further differential oxidation of the more unsaturated HBI. Unfortunately, specific oxidation products of HBI III could not be detected in the strongly oxidized SPM and sediment samples, likely due to their lability towards further oxidation. In contrast, oxidation products of HBI III were detected in weakly oxidized samples of phytoplanktonic cells collected from Commonwealth Bay (also East Antarctica), thus providing more direct evidence for the involvement of photo- and/or autoxidation of HBI III in the region. This oxidative alteration of the ratio IPSO25/HBI III between their source and sedimentary environments might need to be considered more carefully when using this parameter for palaeo sea ice reconstruction purposes in the Antarctic.
Keywords: Alteration of IPSO/HBI III ratio East Antarctica Lipids Near-surface sediments Paleoceanographic implications Photo- and autoxidation Suspended particulate matter
Programme: 1010
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François Fripiat, Daniel M. Sigman, Guillaume Massé, Jean-Louis Tison. (2015). High turnover rates indicated by changes in the fixed N forms and their stable isotopes in Antarctic landfast sea ice (Vol. 120).
Abstract: 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).
Keywords: Antarctic isotopes nitrogen nutrients sea ice
Programme: 1010
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Aurélie Goutte, Yves Cherel, Carine Churlaud, Jean-Pierre Ponthus, Guillaume Massé, Paco Bustamante. (2015). Trace elements in Antarctic fish species and the influence of foraging habitats and dietary habits on mercury levels (Vol. 538).
Abstract: 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 δ13C and δ15N values were determined to investigate whether the fish foraging habitats and dietary habits could explain Hg levels. Species and foraging habitat (δ13C) 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.
Keywords: Heavy metals Nototheniidae Southern Ocean Stable isotopes
Programme: 1010
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J.-F. Rontani, S. T. Belt, Frederic Vaultier, T. A. Brown, G. Massé. (2014). Autoxidative and photooxidative reactivity of highly branched isoprenoid (HBI) alkenes (Vol. 49).
Abstract: 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.
Programme: 1010
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A. Goutte, Y. Cherel, C. Ozouf-Costaz, C. Robineau, J. Lanshere, G. Massé. (2014). Contribution of sea ice organic matter in the diet of Antarctic fishes: a diatom-specific highly branched isoprenoid approach (Vol. 37).
Abstract: New sets of diatom-specific biomarkers, highly branched isoprenoids (HBIs), have been recently proposed to trace carbon flow from ice algae and pelagic phytoplankton to higher trophic level organisms. In the Antarctic, diene, a HBI of sea ice origin was more abundant in ice-associated species, while triene, a HBI of phytoplanktonic origin, was more abundant in pelagic species. However, this HBI approach has never been applied on Antarctic benthic species. Here, we analyzed diene and triene in the liver and the muscle of eight Antarctic coastal fish species (108 specimens). HBI lipids were detected in all specimens, confirming the contribution of sea ice and pelagic organic matter in coastal benthic fish species. Moreover, HBI markers were much more concentrated in the liver than in white muscle, and the relative concentrations of diene and triene strongly varied among species, as a probable result of species differences in feeding habits and trophic ecology. Seasonal variations in HBI concentrations were detected during the whole year in white muscle, but not in the liver. These findings are consistent with the well-known spring bloom in November–December, just before the annual ice break up, and the second proliferation of ice algae during the land-fast ice formation, in April–May. Therefore, investigation of HBI lipids in white muscle will likely shed new light on seasonal changes in the contribution of ice algal-derived organic matter in higher trophic level organisms.
Programme: 1010
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Morin, S., Savarino, J., Bekki, S., Gong, S. and Bottenheim, J. W. (2007). Signature of Arctic surface ozone depletion events in the isotope anomaly (δ17O) of atmospheric nitrate. Atmospheric chemistry and physics, 7, 1451–1469.
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De Angelis, M., J.R. Petit, J. Savarino, R. Souchez, and M.H. Thiemens. (2004). Contributions of an ancient evaporitic-type reservoir to subglacial Lake Vostok chemistry. Earth Planet. Sci. Lett., 222, 751–765.
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McCabe, J.R.; Thiemens, M.H.; Savarino, J. (2007). A record of ozone variability in South Pole Antarctic snow: Role of nitrate oxygen isotopes. J. Geophys. Res., 112.
Abstract: The information contained in polar nitrate has been an unresolved issue for over a decade. Here we demonstrate that atmospheric nitrate's oxygen isotopic composition (?17O-NO3) reflects stratospheric chemistry in winter and tropospheric chemistry in summer. Surface snow isotope mass balance indicates that nitrate oxygen isotopic composition is the result of a mixture of 25% stratospheric and 75% tropospheric origin. Analysis of trends in ?17O-NO3 in a 6 m snow pit that provides a 26-year record reveals a strong 2.70-year cycle that anticorrelates (R = ?0.77) with October–November–December column ozone. The potential mechanisms linking the records are either denitrification or increased boundary layer photochemical ozone production. We suggest that the latter is dominating the observed trend and find that surface ozone and ?17O-NO3 correlate well before 1991 (R = 0.93). After 1991, however, the records show no significant relationship, indicating an altered oxidative environment consistent with current understanding of a highly oxidizing atmosphere at the South Pole. The disappearance of seasonal ?17O-NO3 trends in the surface layer at depth remain unresolved and demand further investigation of how postdepositional processes affect nitrate's oxygen isotope composition. Overall, the findings of this study present a new paleoclimate technique to investigate Antarctic nitrate records that appear to reflect trends in stratospheric ozone depletion by recording tropospheric surface ozone variability.
Keywords: nitrate; isotopes; ozone; 1041 Geochemistry: Stable isotope geochemistry; 0305 Atmospheric Composition and Structure: Aerosols and particles; 3344 Atmospheric Processes: Paleoclimatology; 1610 Global Change: Atmosphere; 0776 Cryosphere: Glaciology
Programme: 1011
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Grannas et al. (2008). An overview of snow photochemistry: evidence, mechanisms and impacts. Atmospheric chemistry and physics, 7.
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