From measurements of Hf-Yb mixtures, we have found that the correction of isobaric interferences involving accepted Yb isotope ratios and reasonable estimates of mass bias result in a significantly under-corrected 176 Hf, which is proportional to the amount of Yb added. This can be explained by (1) a significant difference in the instrumental mass bias between Hf and Yb, and (2) that the accepted values for isotopic ratios within the Yb and/or Hf systems are incorrect. We have evaluated these possibilities by measuring mixed solutions of Yb and Hf on two MC-ICP-MS instruments and undertaking a series of REE fractionation experiments using a thermal ionisation mass spectrometer (TIMS). Our results indicate that the presently accepted abundances of the Yb isotopes are not appropriate. We present new values for Yb isotopic abundances based on the TIMS and MC-ICP-MS results. Using the newly defined Yb values, we demonstrate that Yb and Hf have similar levels of mass bias in plasma ionisation instruments, and that Hf isotope ratios can be used to correct Yb mass bias before subsequent correction of isobaric interference. A laser ablation comparison of Yb and Hf indicates that similar relationships exist, and can be applied to micro-analytical techniques where chemical separation is not possible.

In order to check the heterogeneity of the CI chondrites and determine the average composition of this group of meteorites, we analyzed a series of 6 large chips (weighing between 0.6 and 1.2 g) of Orgueil prepared from 5 different stones. In addition, one sample from each of Ivuna and Alais were analyzed. Although the sizes of the chips used in this study were "large", our results show evidence for minor chemical heterogeneity in Orgueil, particularly for alkali elements and U. After removal of one outlier sample, the spread of the results is considerably reduced. For most of the 46 elements analyzed in this study, the average composition calculated for Orgueil is in very good agreement with previous CI estimates. This average, obtained with a "large" mass of samples, is analytically homogeneous and is suitable for normalization purposes.Finally, the Cu and Zn isotopic ratios are homogeneously distributed within the CI parent body with a spread of less than 100 ppm per atomic mass unit (amu).

International audienceOver the past decades, rare earth elements (REE) and their radioactive isotopes have received tremendous attention in sedimentary geochemistry, as tracers for the geological history of the continental crust and provenance studies. In this study, we report on elemental concentrations and neodymium (Nd) isotopic compositions for a large number of sediments collected near the mouth of rivers worldwide, including some of the world's major rivers. Sediments were leached for removal of non-detrital components, and both clay and silt fractions were retained for separate geochemical analyses. Our aim was to re-examine, at the scale of a large systematic survey, whether or not REE and Nd isotopes could be fractionated during Earth surface processes. Our results confirmed earlier assumptions that river sediments do not generally exhibit any significant grain-size dependent Nd isotopic variability. Most sediments from rivers draining old cratonic areas, sedimentary systems and volcanic provinces displayed similar Nd isotopic signatures in both clay and silt fractions, with Delta epsilon Nd(clay-silt) < vertical bar 1 vertical bar. A subtle decoupling of Nd isotopes between clays and silts was identified however in a few major river systems (e.g. Nile, Mississippi, Fraser), with clays being systematically shifted towards more radiogenic values. This observation suggests that preferential weathering of volcanic and/or sedimentary rocks relative to more resistant lithologies may occur in river basins, possibly leading locally to Nd isotopic decoupling between different size fractions. Except for volcanogenic sediments, silt fractions generally displayed homogeneous REE concentrations, exhibiting relatively flat shale-normalized patterns. However, clay fractions were almost systematically characterized by a progressive enrichment from the heavy to the light REE and a positive europium (Eu) anomaly. In agreement with results from previous soil investigations, the observed REE fractionation between clays and silts is probably best explained by preferential alteration of feldspars and/or accessory mineral phases. Importantly, this finding clearly indicates that silicate weathering can lead to decoupling of REE between different grain-size fractions, with implications for sediment provenance studies. Finally, we propose a set of values for a World River Average Clay (WRAC) and Average Silt (WRAS), which provide new estimates for the average composition of the weathered and eroded upper continental crust, respectively, and could be used for future comparison purposes. (C) 2015 Elsevier Ltd. All rights reserved

Changes in deep ocean ventilation are commonly invoked as the primary cause of lower glacial atmospheric CO2. The water mass structure of the glacial deep Atlantic Ocean and the mechanism by which it may have sequestered carbon remain elusive. Here we present neodymium isotope measurements from cores throughout the Atlantic that reveal glacial–interglacial changes in water mass distributions. These results demonstrate the sustained production of North Atlantic Deep Water under glacial conditions, indicating that southern-sourced waters were not as spatially extensive during the Last Glacial Maximum as previously believed. We demonstrate that the depleted glacial δ13C values in the deep Atlantic Ocean cannot be explained solely by water mass source changes. A greater amount of respired carbon, therefore, must have been stored in the abyssal Atlantic during the Last Glacial Maximum. We infer that this was achieved by a sluggish deep overturning cell, comprised of well-mixed northern- and southern-sourced waters.

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[1] Based on acquired geophysical, geological and geotechnical data and modeling, we suggest hydrate dissolution to cause sediment collapse and pockmark formation in the Niger delta. Very high-resolution bathymetry data acquired from the Niger delta reveal the morphology of pockmarks with different shapes and sizes going from a small ring depression surrounding an irregular floor to more typical pockmarks with uniform depression. Geophysical data, in situ piezocone measurements, piezometer measurements and sediment cores demonstrate the presence of a common internal architecture of the studied pockmarks: inner sediments rich in gas hydrates surrounded by overpressured sediments. The temperature, pressure and salinity conditions of the studied area have allowed us to exclude the process of gas-hydrate dissociation (gas hydrate turns into free gas/water mixture) as a trigger of the observed pockmarks. Based on numerical modeling, we demonstrate that gas-hydrate dissolution (gas hydrate becomes mixture of water and dissolved gas) under a local decrease of the gas concentration at the base of the gas-hydrate occurrence zone (GHOZ) can explain the excess pore pressure and fluid flow surrounding the central hydrated area and the sediment collapse at the border of the GHOZ. The different deformation (or development) stages of the detected pockmarks confirm that a local process such as the amount of gas flow through faults rather than a regional one is at the origin of those depressions. Citation: Sultan, N., et al. (2010), Hydrate dissolution as a potential mechanism for pockmark formation in the Niger delta,

About 3000 years ago, a major vegetation change occurred in Central Africa, when rainforest trees were abruptly replaced by savannas. Up to this point, the consensus of the scientific community has been that the forest disturbance was caused by climate change. We show here that chemical weathering in Central Africa, reconstructed from geochemical analyses of a marine sediment core, intensified abruptly at the same period, departing substantially from the long-term weathering fluctuations related to the Late Quaternary climate. Evidence that this weathering event was also contemporaneous with the migration of Bantu-speaking farmers across Central Africa suggests that human land-use intensification at that time had already made a major impact on the rainforest.

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