Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous‐dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid‐REE‐enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources

Concentrations en terres rares (REE) et composition isotopique du Nd à l'interface fleuve Amazone/océan Atlantique : traçage de processus et bilan

L'estuaire du fleuve Amazone est le siège d'apports colossaux à l'océan en eau continentale, éléments dissous et particules. Cet estuaire est localisé dans une région cruciale dans la circulation des masses d'eau entre les deux hémisphères. Un échantillonnage du fleuve Amazone et de son estuaire, du plateau continental et du large des côtes brésiliennes et guyanaises a été réalisé dans le cadre du projet de recherche AMANDES (ANR/IRD/INSU). Ce projet est intégré dans la catégorie " étude de processus " au programme international GEOTRACES. Ce doctorat a consisté en l'étude des concentrations en terres rares (REE) et de la composition isotopique (CI) du Nd qui sont des traceurs de source, de transport et de processus. Une méthode inédite et très précise de détermination de concentrations en REE par dilution isotopique a été de ce fait développée. Les données obtenues permettent 1)d'observer que la répartition du Nd entre phases dissoutes, colloïdales et particulaires change radicalement entre l'eau de rivière et l'eau de mer 2) de tracer pour la première fois à l'échelle locale et en milieu naturel des apports conséquents en Nd et REE à la phase dissoute et provenant des particules lithogéniques en suspension et déposées sur la marge continentale 3) de compléter la base de données mondiale de ces traceur mettant en évidence pour les eaux antarctiques intermédiaires une signature géochimique contrastant celle habituellement observée au sud de 30°S et qui pourrait être expliquée par des apports provenant des marges continentales. Ces observations appuient des travaux récents d'expérimentation et de modélisation concluant à la sous-estimation des sédiments marinscomme terme source d'éléments dissous à l'océan, terme crucial pour l'étude les cycles géochimiques globaux.The Amazon estuary is a major source of continental waters, dissolved elements and particles. This estuary is located in a crucial area for inter hemispheric water-mass transfers. A sampling of the Amazon and its estuary, the Brazilian and Guyanese margin and offshore waters was made in the framework of the AMANDES (ANR/IRD/INSU) research project. This Project is intregrated in the "process study" topic of the international research program GEOTRACES. This doctorate consisted in the study of rare earth element concentrations (REE) and Nd isotopic compositions both of these being tracers of source, transport and processes. A precise isototopic dilution method for determining the REE concentrations was thus developed. The obtained data allows to 1) observe a radical change in Nd repartition between dissolved particles and colloids from the river water to the seawater; 2) trace for the first time at a local scale and in a natural environment, consequent lithogenic sources of Nd and REE to the dissolved phase from suspended and margin deposited sediments; complete the world database of these tracers thus revealing a contrasted geoquemical signature for the Antarctic Intermediate Waters with that observed south of 30°S and which could be explained by South Atlantic sourced contributions of margin sediment. Recent experimental and modelling works conclude theunderestimation of marine sediments as a source term for the ocean, a term which is crucial for global geoquemical cycles