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 ?g 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.

Abstract: The Cook Ice Cap (CIC) on the sub-Antarctic Kerguelen Islands recently experienced extremely negative surface mass balance. Further deglaciation could have important impacts on endemic and invasive fauna and flora. To put this exceptional glacier evolution into a multi-centennial-scale context, we refined the evolution of the CIC over the last millennium, investigated the associated climate conditions and explored its potential evolution by 2100 ce. A glaciological model, constrained by cosmic ray exposure dating of moraines, historical documents and recent direct mass balance observations, was used to simulate the ice-cap extents during different phases of advance and retreat between the last millennium and 2100 ce. Cosmogenic dating suggests glacial advance around the early Little Ice Age (LIA), consistent with findings from other sub-Antarctic studies, and the rather cold and humid conditions brought about by the negative phase of the Southern Annular Mode (SAM). This study contributes to our currently limited understanding of palaeoclimate for the early LIA in the southern Indian Ocean. Glaciological modelling and observations confirm the recent decrease in CIC extent linked to the intensification of the SAM. Although affected by large uncertainties, future simulations suggest a complete disappearance of CIC by the end of the century.