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The Li/Mg paleothermometer was here updated in a calibration including 15 species of coral from culture or various environmental context, from tropical areas to deep Antarctic waters. This work showed that this new proxy well defines the whole ocean temperature range from -1 to 29°C, with a precision of ± 1.0°C. However, presence of organic matter or diagenetic calcite in the skeleton can bias the reconstructed temperatures. A specific chemical cleaning and micro analysis can overcome these effects. Yet, uncertainties of reconstructed temperatures are higher for tropical corals from shallow waters, largely subjected to seasonal variation of environmental factors (e.g. SST, light, precipitations). Calcification and growth processes of these zooxanthellate species, controlled by their localisation in the lagoon and by seasonal variation, seem to alter the precision of the Li/Mg proxy. By combining Li/Mg and Sr/Ca ratios in a multi-proxy approach, these uncertainties can be considerably reduced, with a precision reaching ± 0.6°C. In a first application, general and local calibrations were compared in order to reconstruct the historical evolution of temperatures from analysis on a Siderastrea siderea, sampled alive in Martinique. The resulting temporal series covers the last two centuries and clearly shows the global warming affecting the Caribbean, in agreement with existing data. A second application was conducted on fossil deep-water corals from Mediterranean Sea, providing the first reconstruction of the temperature evolution of intermediate waters since 55.000 years, with a particularly cold signal during LGM, in response of the last glacial/interglacial cycle.; La calibration du paléo-thermomètre Li/Mg a ici été revisitée pour 15 espèces de corail mises en culture ou issues de contextes environnementaux variés, allant des régions tropicales aux eaux profondes Antarctiques. Ces travaux de thèse ont montré que ce nouveau proxy retrace bien toute la gamme de température de l’océan allant de -1 à 29°C, avec une précision de l’ordre de± 1,0°C. Cependant, la présence dans le squelette de matière organique ou de calcite diagénétique peut biaiser les températures reconstruites. Il a également été montré que ces effets peuvent être corrigés par un nettoyage chimique adapté ou par des analyses spécifiques à micro-échelle. Une analyse des données Li/Mg dans les coraux tropicaux indique que les incertitudes de reconstruction sont plus élevées pour les eaux de surface chaudes et soumises aux variations saisonnières des facteurs environnementaux (SST, lumière, précipitations, etc.). Les processus de calcification ou le mode de croissance de ces espèces à zooxanthelles, contrôlés par leur localisation (lagon) et par les variations saisonnières, semblent altérer la précision du traceur Li/Mg. Toutefois, en combinant les rapports élémentaires Li/Mg et Sr/Ca dans une approche multi-proxy, ces incertitudes peuvent être considérablement réduites, de l’ordre de ± 0,6°C. En première application et après analyse de calibrations globales ou locales, l’évolution historique des températures a été retracée à partir d’une colonie de Siderastrea siderea prélevée vivante en Martinique. La série temporelle obtenue couvrant les 2 derniers siècles trace clairement le réchauffement climatique en cours dans la région des Caraïbes, en accord avec les données existantes. Une seconde application concerne l’utilisation du Li/Mg dans des coraux profonds fossiles de la Mer Méditerranée et permet de reconstruire l’évolution des températures depuis 55 000 ans des eaux intermédiaires de la Méditerranée, tracées particulièrement froides au LGM, et cela en réponse au dernier cycle glaciaire/interlgaciaire.

The coral Li/Mg temperature proxy is revisited through an in-depth trace element analysis of scleractinians collected live from tropical to polar environments. The dataset consists of Li/Ca, Mg/Ca, Sr/Ca and Li/Mg ratios from 64 coral specimens belonging to 8 different taxa, including both reef-building zooxanthellate and cold-water non-zooxanthellate species, from a wide range of water temperature (-1 to 29.5 degrees C), salinity (34.71 to 38.61), and depth (3 to 670m). Our results showed that the reliability of the Li/Mg temperature proxy is strongly limited by the organic matter associated with the coral skeleton, which is most evident within the green bands observed in tropical corals. Organic-rich bands can double the Mg content otherwise present in the skeleton, which may ultimately lead to a temperature overestimation exceeding 15 degrees C. We found that this bias can be overcome by the treatment of coral skeletons with a specific oxidizing cleaning protocol. We also detected the presence of calcite deposits within the aragonite skeleton of some Antarctic living coral specimens, which strongly affects the robustness of the Li/Mg proxy given its temperature sensitivity of similar to 1.5 degrees C/1% calcite. Therefore, to obtain reliable reconstructions a correction needs to be applied when organic matter and/or calcite contamination is present, which requires the scrupulous assessment of the integrity of the aragonite prior to geochemical analyses. Given that some species entrap more organic matter than others, and that some are more prone to calcite contamination, a taxon-related effect is apparent. Here we show that the tropical species Porites spp., Pseudodiploria strigosa and Orbicella annularis, and the cold-water species Madrepora oculata, Caryophyllia antarctica and Flabellum impensum, are all suitable candidates for reconstructing seawater temperatures. The integrated results across a wide temperature range, from extreme cold to tropical shallow waters, yield an overall precision for the Li/Mg-temperature proxy of +/- 1.0 degrees C, as quantified by the standard error of estimates. If calculated from the 95% prediction intervals, the uncertainty of the temperature estimates is +/- 0.9 degrees C at 1 degrees C, +/- 1.5 degrees C at 12 degrees C and +/- 2.6 degrees C at 25 degrees C. However, the uncertainty for the tropical corals (e.g. Porites) can be reduced to +/- 0.6 degrees C if a Li/Mg and Sr/Ca multi-regression approach is applied.

International audience; In contrast to Li/Ca and Mg/Ca, Li/Mg is strongly anticorrelated with temperature in aragonites precipitated by the benthic foraminifer Hoeglundina elegans and a wide range of scleractinian coral taxa. We propose a simple conceptual model of biomineralization that explains this pattern and is consistent with available abiotic aragonite partition coefficients. Under this model the organism actively modifies seawater within its calcification pool by raising its [Ca2+], using a pump that strongly discriminates against both Li+ and Mg2+. Rayleigh fractionation during calcification effectively reverses this process, removing Ca2+ while leaving most Li+ and Mg2+ behind in the calcifying fluid. The net effect of these two processes is that Li/Mg in the calcifying fluid remains very close to the seawater value, and temperature-dependent abiotic partition coefficients are expressed in the biogenic aragonite Li/Mg ratio. We further show that coral Sr/Ca is consistent with this model if the Ca2+ pump barely discriminates against Sr2+. In H. elegans the covariation of Sr/Ca and Mg/Ca requires either that the pump more strongly discriminates against Sr2+, or that cation incorporation is affected by aragonite precipitation rate via the mechanism of surface entrapment. In either case Li/Mg is minimally affected by such ‘vital effects’ which plague other elemental ratio paleotemperature proxies.