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Alain Manceau, Anne-Claire Gaillot, Pieter Glatzel, Yves Cherel, Paco Bustamante. (2021). In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism (Vol. 55).
Abstract: 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.
Programme: 109
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Alain Manceau, Romain Brossier, Sarah E. Janssen, Tylor J. Rosera, David P. Krabbenhoft, Yves Cherel, Paco Bustamante, Brett A. Poulin. (2021). Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science (Vol. 55).
Abstract: 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.
Programme: 109
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Alain Royer, Florent Domine, Alexandre Roy, Alexandre Langlois, Nicolas Marchand, Gautier Davesne. (2021). New northern snowpack classification linked to vegetation cover on a latitudinal mega-transect across northeastern Canada.
Abstract: Changes in mass, extent, duration, and physical properties of snow are key elements for studying associated climate change feedbacks in northern regions. In this study, we analyzed snowpack physical properties along a ‘mega’ transect from 47°N to 83°N (4,000 km) in northeastern Canada, which includes marked transitions between ecozones from boreal forest to subarctic and arctic ecosystems. Our unique dataset of 391 detailed snowpits acquired over the last 20 years, complemented with snow data from weather stations, shows that snowpack properties such as snow water equivalent, snow depth, density, grain size and basal depth hoar fraction (DHF) are strongly linked to vegetation type. Based on these results, we propose an updated classification of snow types in three classes: boreal forest snow (47–58°N), tundra snow (58–74°N) and polar desert snow (74–83°N), which is more appropriate to the study area than the general north hemisphere classification commonly used. We also show that shrub presence along the transect contributes to a significant increase in DHF development which contributes most strongly to the thermal insulation properties of the snowpack. Overall, our analysis suggests that snow–vegetation interactions have a positive feedback effect on warming at northern latitudes.
Keywords: classification de la couverture de neige Gradient latitudinal interactions neige-végétation Latitudinal gradient propriétés de la neige snow cover classification snow–vegetation interaction snowpack properties
Programme: 1042
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Alakkat S. Unnikrishnan, Andrew Matthews, Médéric Gravelle, Laurent Testut, Thorkild Aarup, Philip L. Woodworth, B. Ajay Kumar. (2019). Tide gauges.
Abstract: Tide gauge measurements provide data for routine tidal predictions in ports as well as for extreme events such as storm surges and tsunamis. Along with satellite altimeter measurements, tide gauges also provide measurements used for sea-level rise estimates. This is particularly important for impact assessment in low-lying coastlines of south Asia as well as islands such as the Maldives in the Indian Ocean.
Programme: 688
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Alba Cid, Paula Camus, Sonia Castanedo, Fernando J. Méndez, Raúl Medina. (2017). Global reconstructed daily surge levels from the 20th Century Reanalysis (1871–2010) (Vol. 148).
Abstract: Studying the effect of global patterns of wind and pressure gradients on the sea level variation (storm surge) is a key issue in understanding the recent climate change effect on the dynamical state of the ocean. The analysis of the spatial and temporal variability of storm surges from observations is a difficult task to accomplish since observations are not homogeneous in time, scarce in space, and moreover, their temporal coverage is limited. A recent global surge database developed by AVISO (DAC, Dynamic Atmospheric Correction) fulfilled the lack of data in terms of spatial coverage, but not regarding time extent, since it only includes the last two decades (1992–2014). In this work, we use the 20th Century Reanalysis V2 (20CR), which spans the years 1871 to 2010, to statistically reconstruct daily maximum surge levels at a global scale. A multivariate linear regression model is fitted between daily mean ERA-interim sea level pressure fields and daily maximum surge levels from DAC. Following, the statistical model is used to reconstruct daily surges using mean sea level pressure fields from 20CR. The verification of the statistical model shows good agreements between DAC levels and the reconstructed surge levels from the 20CR. The validation of the reconstructed surge with tide gauges, distributed throughout the domain, shows good accuracy both in terms of high correlations and small errors. A time series comparison is also depicted at specific tide gauges for the beginning of the 20th century, showing a high concordance. Therefore, this work provides to the scientific community, a daily database of maximum surge levels; which correspond to an extension of the DAC database, from 1871 to 2010. This database can be used to improve the knowledge on historical storm surge conditions, allowing the study of their temporal and spatial variability.
Keywords: Climate variability Historical reconstruction Multiple linear regression Statistical modelling Storm surge
Programme: 688
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Alba Zanini, Silvia Vernetto, Vicente Ciancio, Gustavo Di Giovan, Paolo Morfino, Alessandro Liberatore, Gianrossano Giannini, Guillaume Hubert. (2019). Environmental radiation dosimetry at high southern latitudes with Liulin type instruments (Vol. 208-209).
Abstract: Because of the geomagnetic field shape, the polar regions are the most exposed to secondary particles and radiation produced by primary cosmic rays in the atmosphere. At present, only few experimental measurements of environmental dose are reported in literature at high southern latitudes. A three year campaign has been carried out in two different locations, Ushuaia (Argentina, 54.80∘ S, 68.30∘ W) and Marambio (Antarctica, 64.24∘ S, 56.63∘ W), using a Liulin type detector, allowing to measure the total environmental radiation flux and dose. The Liulin type instrument, measuring the energy deposition in a silicon detector, is especially suitable to evaluate the dose, separating the low and high LET (Linear Energy Transfer) components. The instrument was installed at the GAW Station in Ushuaia and inside the LAMBI Laboratory at the Marambio Antarctic base. In December 2017 preliminary measurements have been carried out at the French-Italian base Dome C, at 3233 m a.s.l., with a Liulin-AR, a new version of Liulin spectrometer, specifically built for this application by the Space Research and Technology Institute of Bulgarian Academy of Sciences. In this paper the environmental dose values obtained in the different southern high latitude locations are compared and discussed.
Keywords: Antarctic Cosmic rays Dosimetry High latitudes Liulin
Programme: 1112
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Albane Barbero, Camille Blouzon, Joël Savarino, Nicolas Caillon, Aurélien Dommergue, Roberto Grilli. (2020). A compact incoherent broadband cavity-enhanced absorption spectrometer for trace detection of nitrogen oxides, iodine oxide and glyoxal at levels below parts per billion for field applications (Vol. 13). Bachelor's thesis, , .
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Albane Barbero, Roberto Grilli, Markus M. Frey, Camille Blouzon, Detlev Helmig, Nicolas Caillon, Joël Savarino. (2022). Summer variability of the atmospheric NO2 : NO ratio at Dome C on the East Antarctic Plateau (Vol. 22).
Abstract: Previous Antarctic summer campaigns have shown unexpectedly high levels of oxidants in the lower atmosphere of the continental plateau and at coastal regions, with atmospheric hydroxyl radical (OH) concentrations up to 4 × 106 cm−3. Such high reactivity in the summer Antarctic boundary layer results in part from the emissions of nitrogen oxides (NOx ≡ NO + NO2) produced during photo-denitrification of the snowpack, but its underlying mechanisms are not yet fully understood, as some of the chemical species involved (NO2, in particular) have not yet been measured directly and accurately. To overcome this crucial lack of information, newly developed optical instruments based on absorption spectroscopy (incoherent broadband cavity-enhanced absorption spectroscopy, IBBCEAS) were deployed for the first time at Dome C (−75.10 lat., 123.33 long., 3233 m a.s.l.) during the 2019–2020 summer campaign to investigate snow–air–radiation interaction. These instruments directly measure NO2 with a detection limit of 30 pptv (parts per trillion by volume or 10−12 mol mol−1) (3σ). We performed two sets of measurements in December 2019 (4 to 9) and January 2020 (16 to 25) to capture the early and late photolytic season, respectively. Late in the season, the daily averaged NO2:NO ratio of 0.4 ± 0.4 matches that expected for photochemical equilibrium through Leighton's extended relationship involving ROx (0.6 ± 0.3). In December, however, we observed a daily averaged NO2:NO ratio of 1.3 ± 1.1, which is approximately twice the daily ratio of 0.7 ± 0.4 calculated for the Leighton equilibrium. This suggests that more NO2 is produced from the snowpack early in the photolytic season (4 to 9 December), possibly due to stronger UV irradiance caused by a smaller solar zenith angle near the solstice. Such a high sensitivity of the NO2:NO ratio to the sun's position is of importance for consideration in atmospheric chemistry models.
Programme: 1177
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Albenne C., Skov L.K., Mirza O., Gajhede M., Feller G., D’Amico S., André G., Potocki Veronese G., Van der Veen B.A., Monsan P. & Remaud-Siméon M. (2004). Molecular basis of the amylose-like polymer formation catalyzed by Neisseria polysaccharea amylosucrase. J. Biol. Chem., 279, 726–734.
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Albertin, S., Savarino, J., Bekki, S., T. Roberts, T., Barret, B., Mao, J., Simpson, W., Law, K. (2021). Isotopic constraints on the sources and fate of atmospheric nitrate in Fairbanks, Alaska: preliminary results of the pre-ALPACA campaign.
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