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Neodymium (Nd) isotopes have been utilized as a tracer of water mass source in the modern ocean and in palaeoceanographic studies, though the oceanic cycling of Nd is not yet fully constrained. Recent studies have highlighted the importance of processes that occur near the seawater – sediment interface in altering the Nd isotopic composition of bottom waters. The two major observed processes “boundary exchange” and “benthic flux” have been suggested as playing an important role in setting water mass compositions, however, more studies are needed to constrain their chemical mechanism and the extent to which these processes set the composition of deep waters. The Antarctic continental margin is an important place to study these processes because Antarctic-sourced waters dominate the Southern Ocean and ventilate the global deep ocean. This study is the first to measure and compare seawater, porewater and sediment data from along the margin of Antarctica to examine the nature of potential boundary processes. We show that a process similar to boundary exchange seems to be occurring within porewaters, modifying porewater chemistry by shifting its Nd isotopic ratios to more radiogenic values without significantly increasing the concentration of dissolved Nd. We hypothesize that this shift results from partial dissolution of radiogenic detrital particles, such as smectite, amphibole and/or volcanic glass, while re-scavenging maintains low Nd concentrations. We infer the existence of benthic flux of porewaters to deep waters by examining chemical gradients in porewaters and show that it is much lower on the Antarctic Margin compared to other studies. Benthic flux appears to be slightly enhanced along the Antarctic Peninsula than in the Bellingshausen Sea due to partial degradation of organic matter and associated dissolution of Fe-Mn oxyhydroxides. Taken together, boundary processes do not significantly change the Nd isotopic composition of Antarctic margin seawater because while the porewaters have an altered Nd isotopic composition the Nd concentration of these porewaters is low compared to other settings.

Significant gaps in our understanding of the oceanic cycling of neodymium (Nd) and the other rare earth elements (REEs) remain despite decades of research. One important observation which has not been adequately explained is that the concentration of dissolved Nd typically increases with depth, similar to nutrient profiles, while Nd isotopes appear to reflect conservative water mass mixing in the intermediate and deep ocean; this has been termed the “Nd paradox”. Here we present a detailed study of the dissolved Nd isotopic composition across a section at 40°S in the South Atlantic, collected by UK GEOTRACES cruise (section GA10). The South Atlantic represents a natural laboratory for our understanding of spatial controls on ocean geochemistry, because of the large variability of inputs, spatial differences in particulate cycling, and horizontal advection and mixing at depth between major northern- and southern-sourced water masses. This variability has also made the South Atlantic a critical region subject to intense investigations that aim at reconstructing past changes in ocean processes, such as changes in biological productivity and deep ocean circulation. Our Nd isotope results from the GA10 section provide observational data show the signal of water mass mixing and reversible scavenging. In the surface ocean (0–600 m), Nd isotopic compositions are distinct between different surface ocean currents and spatially can be tied to various continental sources. In the intermediate ocean (600–2500 m), the vertical Nd isotope distribution exhibits distinct signals of different water masses by horizontal advection, including upper North Atlantic Deep Water and Antarctic Intermediate Water formed in the Atlantic Ocean or the Indian Ocean. The Nd isotope distribution also reflects influence of reversible scavenging that smears the signals downwards in the water column (i.e., offset to more radiogenic values). In the deep ocean below 2500 m, Nd isotope distribution largely follows conservative water mass mixing model. Nd concentration in the deep ocean, however, deviates from conservative mixing and increases constantly with depth. We also observe that Nd isotopes appear to be shifted towards the composition of overlying water masses. These observations suggest that reversible scavenging of Nd onto organic and other types of particles is a major vertical process throughout the water column. We also suggest that this process can resolve the “Nd paradox” of decoupling of Nd concentration and isotopic composition due to mixing dynamics. Because abyssal water masses already have a high Nd concentration, a given amount of Nd added from the vertical process has less of an effect on Nd isotopic compositions in deep water masses than it does for intermediate water masses which have comparatively low Nd concentration.

The Nordic Seas are the primary location where the warm waters of the North Atlantic Current densify to form North Atlantic Deep Water, which plays a key part in the modern Atlantic Meridional Overturning Circulation. The formation of dense water in the Nordic Seas and Arctic Ocean and resulting ocean circulation changes were probably driven by and contributed to the regional and global climate of the last glacial maximum (LGM). Here we map the source and degree of mixing of deep water in the Nordic Seas and through the Arctic Gateway (Yermak Plateau) over the past 35 thousand years using neodymium isotopes (εNd) measured on authigenic phases in deep-sea sediments with a high spatial and temporal resolution. We find that a large-scale reorganization of deep-water formation in the Nordic Seas took place between the LGM (23–18 thousand years ago) and the rapid climate shift that accompanied the subsequent deglaciation (18–10 thousand years ago). We show that homogeneous εNd signatures across a wide range of sites support LGM deep-water formation in the Nordic Seas. In contrast, during the deglaciation, disparate and spatially variable εNd values are observed leading to the conclusion that deep-water formation may have been reduced during this time.

International audience; Chemical weathering plays an important role in sequestering atmospheric CO2, but its potential influence on global climate over geological timescales remains debated. To some extent, this uncertainty arises from the difficulty in separating the respectivecontribution of sedimentary and crystalline silicate rocks to past weathering rates in the geological record; two types of rocks having presumably different impact on the long-term carbon cycle. Here, we present a novel method for tracing the origin of weathered rocks on continents, based on the measurement of REE and Nd isotopes (eNd) in leached iron oxide fractions of river sediments [1,2]. We show that the degree of mid-REE enrichment in leached sediment phases provides information on the source of Fe oxides, indicating the presence of ancient marine Fe oxides derived from the erosion of sedimentary rocks or more recent secondary oxides formed in soils via silicate weathering. We also demonstrate that the e Nd difference between paired Fe-oxide and detrital fractions in river sediments (DeNd Feox-Det) reflects the relative contribution of sedimentary vs crystalline silicate rocks during weathering. Rivers draining old cratons and volcanic provinces display near-zero DeNd Feox-Det values indicative of dominant silicate weathering (0.5 ± 1.1), while multi-lithological catchments hosting sedimentary formationsyield systematically higher values (2.7 ± 1.2). Taken together, these findings show that sedimentary rock weathering can be traced by the occurrence of riverine Fe oxides having more radiogenic Nd isotope signatures compared to detrital fractions. Finally, the influence of climate and geomorphic parameters on the Nd isotopic composition of sedimentary Fe oxides will be discussed, together with future perspectives.

Riverine suspended particulate matter (SPM) is essential for the delivery of micronutrients such as iron (Fe) to the oceans. SPM is known to consist of multiple phases with differing reactivity, but their role in the delivery of elements to the oceans is poorly constrained. Here we provide new constraints on the source and composition of reactive phases in SPM from the Mackenzie River, the largest sediment source to the Arctic Ocean. Sequential leaching of SPM shows that river sediments contain labile Fe phases. We estimate the labile Fe flux is substantial (0.21(+0.06,−0.05) Tg/yr) by quantifying Fe concentrations in weak leaches of the SPM. The labile Fe phase hosts a considerable amount of rare earth elements (REE), including neodymium (Nd). We demonstrate that the labile Fe phase and dissolved load have radiogenic Nd isotope ratios that are identical within uncertainty, but up to 8 epsilon units distinct from the silicate phase. We interpret this as evidence for dynamic cycling between Fe-oxide phases in SPM and the river water, demonstrating the high reactivity of the labile Fe phase. Nd isotope and elemental molar ratios suggest that a significant amount of labile Fe- and Nd-bearing phases are derived from Fe-oxides within the sedimentary source rock rather than silicate mineral dissolution. Thus, sedimentary rock erosion and weathering provides an important source of labile Fe, manganese (Mn) and by extension potentially other trace metals. Our results imply that both past and future environmental change in the Arctic, such as permafrost thaw, may trigger changes to the supply of reactive trace metals. These results demonstrate that a re-evaluation of sediment reactivity within rivers is required where uplifted sedimentary rocks are present.

Significant gaps in our understanding of the oceanic cycling of neodymium (Nd) and the other rare earth elements (REEs) remain despite decades of research. One important observation which has not to date been adequately explained is that the concentration of dissolved Nd typically increases with depth, similar to nutrient profiles, while Nd isotopes appear to reflect conservative water mass mixing in the intermediate and deep ocean; this has been termed the “Nd paradox”. Here we present a detailed study of the dissolved Nd isotopic composition across a section at 40°S in the South Atlantic, collected by UK GEOTRACES cruise (section GA10). The South Atlantic represents a natural laboratory for our understanding of spatial controls on ocean geochemistry, because of the large variability of inputs, spatial differences in particulate cycling, and horizontal advection and mixing at depth between major northern- and southern- sourced water masses. This variability has also made the South Atlantic a critical region for reconstructing past changes in ocean processes such as changes in biological productivity and deep ocean circulation, using paleoceanographic proxies such as foraminiferal carbon and Nd isotopes.This GA10 section of Nd isotopes provides observational data showing chemical changes across water mass boundaries as a result of the horizontal advection of water mass chemistry by ocean circulation but also containing the imprint of reversible scavenging as the major vertical process. In the surface ocean (0 - 600 m), Nd isotopic compositions are distinct between different surface ocean currents and spatially can be tied to various continental sources. In the intermediate ocean (600 - 2500 m), the vertical Nd isotope distribution exhibits distinct signals of different water masses (i.e. a-AAIW, i-AAIW, and u-NADW) by horizontal advection, as well as influence of reversible scavenging that smears the signals downwards (i.e. offset to more radiogenic values). In the deep ocean below 2500 m, Nd isotope distribution follows conservative water mass mixing model. Nd concentration in the deep ocean, however, deviates from conservative mixing and increases constantly with depth. We also observe that Nd isotopes appear to be shifted towards the composition of overlying water masses. These observations suggests that reversible scavenging onto organic and other types of particles is a major vertical process throughout the water column. We also suggest that this process can resolve the “Nd paradox” of decoupling of Nd concentration and isotopic composition because abyssal water masses already have a high [Nd], so that a given amount of added Nd has less effect on ƐNd in deep water masses than it does for low [Nd] intermediate water masses.

Rivers carry the dissolved and solid products of silicate mineral\ud weathering, a process that removes CO2 from the atmosphere and\ud provides a key negative climate feedback over geological timescales.\ud Here we show that in some river systems, a reactive exchange pool\ud on river suspended particulate matter, bonded weakly to mineral\ud surfaces, increases the mobile cation flux by 50%. The chemistry\ud of both river waters and the exchange pool demonstrate exchange\ud equilibrium, confirmed by Sr isotopes. Global silicate weathering\ud fluxes are calculated based on riverine dissolved sodium (Na+) from\ud silicate minerals. The large exchange pool supplies Na+ of non-\ud silicate origin to the dissolved load, especially in catchments with\ud widespread marine sediments, or where rocks have equilibrated with\ud saline basement fluids. We quantify this by comparing the riverine\ud sediment exchange pool and river water chemistry. In some basins,\ud cation exchange could account for the majority of sodium in the\ud river water, significantly reducing estimates of silicate weathering.\ud At a global scale, we demonstrate that silicate weathering fluxes\ud are over-estimated by 12-28%. This over-estimation is greatest in\ud regions of high erosion and high sediment loads where the negative\ud climate feedback has a maximum sensitivity to chemical weathering\ud reactions. In the context of other recent findings that reduce the\ud net CO2 consumption through chemical weathering, the magnitude\ud of the continental silicate weathering fluxes and its implications for\ud solid Earth CO2 degassing fluxes needs to be further investigated.

Chemical weathering plays an important role in sequestering atmospheric CO2, but its potential influence on global climate over geological timescales remains debated. To some extent, this uncertainty arises from the difficulty in separating the respective contribution of sedimentary and crystalline silicate rocks to past weathering rates in the geological record; two types of rocks having presumably different impact on the long-term carbon cycle. In this study, we investigate the use of rare earth element (REE) and neodymium isotopes (εNd) in leached iron oxide fractions of river sediments for tracing the origin of weathered rocks on continents. A new index, called ‘concavity index’ (CI), is defined for measuring the degree of mid-REE enrichment in geological samples, which enables the determination of the source of iron oxides in sediments, such as seawater-derived Fe-oxyhydroxide phases, ancient marine Fe oxides derived from the erosion of sedimentary rocks, and recent secondary oxides formed in soils via alteration of crystalline silicate rocks or pyrite oxidation. Using this index, we demonstrate that the εNd difference between paired Fe-oxide and detrital fractions in river sediments (defined here as ∆εNd Feox-Det) directly reflects the relative contribution of sedimentary versus crystalline silicate rocks during weathering. While rivers draining old cratons and volcanic provinces display near-zero ∆εNd Feox-Det values indicative of dominant silicate weathering (0.5 ± 1.1; n = 30), multi-lithological catchments hosting sedimentary formations yield systematically higher values (2.7 ± 1.2; n = 44), showing that sedimentary rock weathering can be traced by the occurrence of riverine Fe oxides having more radiogenic Nd isotope signatures compared to detrital fractions. This assumption is reinforced by the evidence that calculated ∆εNd Feox-Det values agree well with previous estimates for carbonate and silicate weathering rates in large river basins. Examining the influence of climate and tectonics on measured Nd isotopic compositions, we find that ∆εNd Feox-Det is strongly dependent on temperature in lowlands, following an Arrhenius-like relationship that reflects enhanced alteration of silicate rocks and formation of secondary Fe oxides in warmer climates. In contrast, in high-elevation catchments, ∆εNd Feox-Det defines striking correlation with maximum basin elevation, which we also interpret as reflecting the intensification of silicate weathering and associated Fe oxide formation as elevation decreases, due to the combined effects of thicker soils and warmer temperature. Overall, our new findings are consistent with previous assertions that the alteration of sedimentary rocks prevails in high-elevation environments, while silicate weathering dominates in floodplains. This novel approach combining REE and Nd isotopes opens new perspectives for disentangling the weathering signals of sedimentary and crystalline silicate rocks in the geologic record, which could be used in future studies to reassess the causal relationships between mountain uplift, erosion and climate throughout Earth's history.

A large portion of freshwater and sediment is exported to the ocean by just several of the world's major rivers. Many of these mega-rivers are under significant anthropogenic pressures, such as damming and sand mining, which are having a significant impact on water and sediment delivery to deltaic ecosystems. However, accurately measuring the total sediment flux and its mean physicochemical composition is difficult in large rivers due to hydrodynamic sorting of sediments. To account for this, we developed an updated semi-empirical Rouse modeling framework, which synoptically predicts sediment concentration, grain size distribution, and mean chemical composition (organic carbon wt%, Al/Si ratio) with depth and across the river channel.We applied this model to derive new sediment flux estimates for the Irrawaddy and the Salween, the last two free-flowing mega-rivers in Southeast Asia, using a newly collected set of suspended sediment depth samples, coupled to ADCP-measured flow velocity data. Constructing sediment-discharge rating curves, we calculated an annual sediment flux of 326 (68% confidence interval of 256-417) Mt/yr for the Irrawaddy and 159 (109-237) Mt/yr for the Salween, together accounting for 2-3% of total global riverine sediment discharge. The mean flux-weighted sediment exported by the Irrawaddy is significantly coarser (D84 = 193 ± 13 µm) and OC-poorer (0.29 ± 0.08 wt%) compared to the Salween (112 ± 27 µm and 0.59 ± 0.16 wt%, respectively). Both rivers export similar amounts of particulate organic carbon, with a total of 1.9 (1.0-3.3) Mt C/yr, contributing ~1% of the total riverine POC export to the ocean. These results underline the global significance of the Irrawaddy and Salween rivers and warrant continued monitoring of their sediment fluxes, given the increasing anthropogenic pressures on these river basins.

A large portion of freshwater and sediment is exported to the ocean by a small number of major rivers. Many of these megarivers are subject to substantial anthropogenic pressures, which are having a major impact on water and sediment delivery to deltaic ecosystems. Due to hydrodynamic sorting, sediment grain size and composition vary strongly with depth and across the channel in large rivers, complicating flux quantification. To account for this, we modified a semi‐empirical Rouse model, synoptically predicting sediment concentration, grain‐size distribution, and organic carbon (%OC) concentration with depth and across the river channel. Using suspended sediment depth samples and flow velocity data, we applied this model to calculate sediment fluxes of the Irrawaddy (Ayeyarwady) and the Salween (Thanlwin), the last two free‐flowing megarivers in Southeast Asia. Deriving sediment‐discharge rating curves, we calculated an annual sediment flux of urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0001 Mt/year for the Irrawaddy and urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0002 Mt/year for the Salween, together exporting 46% as much sediment as the Ganges‐Brahmaputra system. The mean flux‐weighted sediment exported by the Irrawaddy is significantly coarser (D84 = 193 ± 13 μm) and OC‐poorer (0.29 ± 0.08 wt%) compared to the Salween (112 ± 27 μm and 0.59 ± 0.16 wt%, respectively). Both rivers export similar amounts of particulate organic carbon, with a total of urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0003 Mt C/year, 53% as much as the Ganges‐Brahmaputra. These results underline the global significance of the Irrawaddy and Salween rivers and warrant continued monitoring of their sediment flux, given the increasing anthropogenic pressures on these river basins.