Description: Highlights • First systematic dissolved neodymium isotope distributions in Angola and Cape Basins. • Deep water neodymium isotopes dominated by conservative mixing in study area. • Neodymium isotopes trace surface waters from Mozambique Channel in Angola Basin. • Cape Basin bottom water neodymium isotopes are unaffected by neodymium from sediments. • Glacial Cape Basin bottom waters may show effects of sedimentary neodymium inputs. Abstract In contrast to the vigorous deep ocean circulation system of the north- and southwestern Atlantic Ocean, no systematically sampled datasets of dissolved radiogenic neodymium (Nd) isotope signatures exist to trace water mass mixing and provenance for the more restricted and less well ventilated Angola Basin and the Cape Basin in the southeastern Atlantic Ocean, where important parts of the return flow of the Atlantic Meridional Overturning Circulation are generated. Here, to improve our understanding of water mass mixing and provenance, we present the first full water column Nd isotope (expressed as εNd values) and concentration data for a section across the western Angola Basin from 3° to 30° S along the Zero Meridian and along an E-W section across the northern Cape Basin at 30° S sampled during GEOTRACES cruise GA08. Compared with the southwestern Atlantic basin we find overall less radiogenic εNd signatures reaching −17.6 in the uppermost 200 m of the Angola and Cape basins. In the western Angola Basin these signatures are the consequence of the admixture of a coastal plume originating near 13° S and carrying an unradiogenic Nd signal that likely resulted from the dissolution of Fe-Mn coatings of particles formed in river estuaries or near the West African coast. The highly unradiogenic Nd isotope signatures in the upper water column of the northern Cape Basin, in contrast, originate from old Archean terrains of southern Africa and are introduced into the Mozambique Channel via rivers like the Limpopo and Zambezi. These signatures allow tracing the advection of shallow waters via the Agulhas and Benguela currents into the southeastern Atlantic Ocean. The Nd isotope compositions of the deep water masses in both basins primarily reflect conservative water mass mixing with the only exception being the central Angola Basin, where the signatures are significantly overprinted by terrestrial inputs. Bottom waters of the Cape Basin show excess Nd concentrations of up to 6 pmol/kg (20%), originating from resuspended bottom sediments and/or dissolution of dust, but without significantly changing the isotopic composition of the waters due to similar εNd values of particles and bottom waters ranging between −9.6 and −10.5. Given that bottom waters within the Cape Basin today are enriched in Nd, non-conservative Nd isotopic effects may have been resolvable under past glacial boundary conditions when bottom waters were more radiogenic.

Description: The sedimentary concentration and stable isotope composition of molybdenum (Mo) is widely used as a proxy for paleo redox conditions in the marine environment. However, the behavior of Mo during early diagenesis is still not fully understood, which complicates the application of the Mo proxy in ancient continental margin environments. Here, we present Mo concentrations and isotope compositions of sediment and pore water samples from the Guaymas Basin in the Gulf of California. Our sample set covers a broad range of depositional environments, including sediments from within the eastern equatorial Pacific oxygen minimum zone (OMZ), from a semi-restricted oxic graben, and from near a hydrothermal vent-field. By investigating Mo cycling in these different settings, we provide new insights into different modes of Mo fixation and the associated isotope fractionation. Sediments from the OMZ have authigenic Mo concentrations (Moauth) between 3.3 and 17.2 µg/g and δ98Mo between +1.64 and +2.13 ‰. A linear decrease in pore water Mo concentrations to the depth were hydrogen sulfide accumulates along with sedimentary authigenic δ98Mo values (δ98Moauth) close to seawater indicate diffusion of Mo from the bottom water into the sediment with little isotope fractionation during quantitative Mo removal. Sediments from the site with oxic bottom water within the basin reveal Moauth concentrations ranging from 1.2 to 14.7 µg/g and δ98Moauth signatures between –1.39 to +2.07 ‰. Pore water Mo concentrations are generally higher than ambient bottom water concentrations and the light δ98Moauth signatures of the pore waters between +0.50 and +0.80 ‰ and of the sediments indicate continuous Mo exchange between the pore water Mo pool and Mn and Fe oxides during early diagenesis. Sediment samples from the vent field mainly consist of black smoker debris and are characterized by Moauth concentrations ranging from 8.6 to 33.2 µg/g and δ98Moauth values as high as +2.20 ‰. The relatively high Mo concentrations and seawater-like δ98Mo can be explained by near-quantitative Mo scavenging from hydrothermal solutions with little isotope fractionation at high temperatures. Comparison of our new data for the OMZ sediments in the Gulf of California with previously published data for sediments from the Peruvian OMZ highlights that Mo isotope compositions in this kind of setting strongly depend on how Mo is delivered to the sediment. If Mo delivery into the sediment contributes to Mo accumulation in the solid phase, as is the case in the Guaymas Basin, sedimentary Moauth concentrations are relatively low but the isotope values are close to the δ98Mo signal of seawater. If Mo is exclusively delivered by particles, like on the Peruvian margin, much higher sedimentary Moauth concentrations can be attained. In the latter case, Moauth isotope values will be lighter because the sediments preserve the isotopic offset that was generated during adsorption or uptake of Mo by particles. Our findings de-emphasize the role of dissolved Mo speciation in pore waters but highlight the importance of the mode of Mo delivery for the Mo concentration and isotope composition preserved in the paleo-record.

Description: Highlights • Exchange between pore and bottom water with sediment affects authigenic REE in the Labrador Sea (LS). • REE-based correction allows reconstruction of past bottom water ϵNd signatures. • Evidence for lack of southern sourced water in the LS through the last 35 ka. • Glacial LS bottom waters were less radiogenic than today with ϵNd = −16 ± 1. • Similarity to Nordic Seas ϵNd record suggests uninterrupted supply of overflow waters. Abstract Deep waters of the Labrador Sea (LS) are important contributors to the Atlantic Meridional Overturning Circulation, but their water mass structure has been highly variable and sensitive to climatic changes on different time scales. The LS is also an area of intense exchange of rare earth elements (REE) between seawater and the underlying sediments, which complicates the reconstruction of past deep water provenance based on radiogenic neodymium (Nd) isotopes. Most notably, Northwest Atlantic Bottom Water exchanges Nd with Archaean age Laurentian detritus, resulting in a significant shift to less radiogenic Nd isotope signatures before it enters the North Atlantic to form the deep part of North Atlantic Deep Water. Here we show that the authigenic fractions of LS core top sediments carry Nd isotope signatures intermediate between bottom water and detritus and thus reflect pore waters that incorporate a mixture of both signatures. We furthermore find that detrital imprints on pore waters led to shifts of REE patterns in the authigenic fraction towards detrital signatures in the past during times of enhanced supply of glacially eroded material from Hudson Bay to the LS, as recorded by radiogenic lead isotopes. This allows an estimation of the intensity of past benthic REE exchange inside the LS. We exploit variations in the mid REE enrichment in the authigenic phase to propose a correction to one LS Nd isotope record for detrital imprints originating from pore water exchange. The corrected ϵNd signatures are argued to more accurately reflect those of past bottom waters. This correction results in past LS bottom water signatures of −16 ± 1 during MIS 2 and 3, considerably less radiogenic than today. This implies that no southern sourced waters advanced into the LS during the last 35 ka and instead supports continuous bottom water sourcing from the Nordic Seas. It thus seems likely that LS bottom waters supplied unradiogenic Nd to abyssal Glacial North Atlantic Bottom Water in the Northwest Atlantic, as was previously hypothesized.

Description: Highlights • Improved understanding of the behaviour of instrumental mass fractionation (IMF). • The effect of matrix elements on IMF is largely associated with plasma conditions that can be quantified with the NAI. • Matrix effects can be systematically and significantly attenuated by tuning of instrumental operating parameters. • A matrix tolerance plasma state is defined for stable barium isotope analysis. • The suggested analytical protocol is expected to be applicable to other stable isotope measurements with MC-ICP-MS. Abstract Stable barium isotope measurements with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) remain an analytical challenge and can be considerably affected by the presence of matrix elements, even when applying double spiking. Therefore significant efforts were invested in previous studies to develop efficient barium purification methods. However, due to the high variability in matrix/barium ratios for diverse sample matrices, potential matrix effects can still not be excluded. While a lot of effort has been invested into improving the chemical separation protocols, the impact of plasma conditions on the accuracy and precision of stable isotope measurements has rarely been considered. Here we present a systematic investigation of the relationship between plasma conditions, instrumental mass fractionation (IMF) and impurity (i.e. matrix) concentrations. The Normalised Ar Index (NAI) and Matrix-Ar Index (MA) are used to quantify MC-ICP-MS plasma conditions and plasma mass loading, respectively. Our results show that the effect of matrix elements on IMF is largely linked to plasma conditions (i.e. NAI) and behaves as a linear function of mass loading (i.e. MA). Accordingly, the matrix effects can be significantly attenuated by increasing the NAI thereby minimising the risk of plasma “over-loading”. The improved understanding of the behaviour of the matrix-induced IMF allows us to define a matrix tolerance plasma state for barium isotope analysis. The accuracy of this recommended method is further assessed by analyses of two well-studied reference materials, the GEOTRACES seawater reference sample SAFe D2 and the carbonate reference material JCp-1. We expect that the analytical protocol described in this study is applicable not only to barium isotope analysis, but also to a wide range of other stable isotope measurements with MC-ICP-MS.

Description: The marine chromium (Cr) cycle is still insufficiently understood, in particular the mechanisms modulating the spatial distribution of dissolved stable Cr isotopes in seawater. Redox transformations between its main oxidation states, Cr(VI) and Cr(III), have been held accountable for the observed tight inverse logarithmic relationship between the dissolved Cr concentration [Cr] and its isotopic composition (δ53Cr), whereby isotopically light Cr(III) is removed in surface waters and oxygen minimum zones (OMZs), and subsequently released to deeper waters from remineralized particles or sediments. Seawater [Cr] and δ53Cr were investigated in a series of depth profiles across the Peruvian margin OMZ, covering a wide spectrum of dissolved oxygen concentrations ranging from 2 to 242 µmol/kg. We found [Cr] ranging from 1.5 to 5.5 nmol/kg, associated with δ53Cr variations between +1.59 and +0.72 ‰, but no systematic relationship to dissolved oxygen concentrations. However, distinctly different seawater profiles were observed above the suboxic/anoxic shelf compared to those located further offshore, with substantial Cr removal restricted to suboxic or anoxic environments on the shelf. This suggests that suboxic conditions ([O2] 〈 5 µmol/kg) alone are not sufficient to account for substantial Cr removal. Given that environmental conditions under which Cr can be reduced remain restricted spatially, the role of this sink in the marine Cr cycle may therefore be small. Additionally, some observations corroborate the assumption that Cr reduction is not necessarily accompanied by immediate adsorption of the formed Cr(III) onto particles, leading to its removal from the dissolved phase. Instead, partial removal of Cr(III) via particles, leaving a residual dissolved Cr(III) pool, may be more widespread in suboxic waters.

Description: Enabled by the success in the determination of stable barium (Ba) isotopic compositions in seawater, Ba isotopes have been suggested as a novel tool to study physical and biogeochemical processes in the present and past ocean. However, a better understanding of the fractionation of Ba isotopes during particle-seawater interactions is a prerequisite for such applications. In this study, we use an extensive data set of concentrations and isotopic compositions of dissolved Ba (DBa and δ138BaDBa) and bulk particulate Ba (pBabulk and δ138BapBabulk) collected in the northern South China Sea (NSCS) to constrain Ba isotope fractionation in the upper ocean. Seawater and suspended particle samples for Ba isotope measurements were collected in January 2010 along a transect from the outer shelf to the lower slope. The water column profiles reaching depths of 1000 m are characterized by a general decrease of δ138BaDBa and an increase of DBa with depth. However, δ138BaDBa signatures are essentially constant at +0.6‰ in the upper 150 m of the entire study area. The corresponding δ138BapBabulk, which primarily represents the isotopic compositions of oceanic or excess particulate Ba (pBaxs), is consistently lower than δ138BaDBa but also constant at values of +0.1 to +0.2‰. This suggests that the same Ba isotope fractionation process prevails above 150 m on the NSCS outer shelf and slope resulting in a constant in situ fractionation factor of −0.5‰. This value is consistent with previously reported values of −0.4 to −0.5‰ in the upper 200 m of the open ocean and a lake. Moreover, we observe significant differences of pBaxs distributions from those of particulate calcium, particulate organic carbon and nitrogen, and biogenic silica indicating that passive adsorption onto particles rather than active biological utilization is most likely the primary process inducing Ba isotope fractionation in the upper NSCS. The constant δ138BapBabulk signatures suggest that particulate Ba isotopes integrate reliable information during transformation of DBa to pBaxs and are thus a more robust proxy for total particle fluxes than pBaxs concentrations, which show variable values potentially affected by other processes (e.g., particle sinking and/or zooplankton grazing) and thus reflects “snapshot” processes in the water column. We contend that biological productivity plays only a subordinate role in regulating the surface Ba isotopic composition of bulk suspended particles. The extent to which Ba isotopes may nevertheless be a reliable proxy for present and past export productivity requires further analyses of the δ138Ba signature of specific Ba carriers such as barite throughout the water column and in the sediments.

Description: Highlights • Nd isotope records from the South Atlantic and Southern Ocean. • New Early Cretaceous general circulation model. • Opening history of gateways on the Falkland Plateau. • Gateway opening controlled organic carbon burial. Organic carbon burial is an important driver of carbon cycle and climate dynamics on geological and shorter time scales. Ocean basins emerging during the Early Cretaceous break-up of Gondwana were primary sites of organic carbon burial, implying that their tectonic and oceanographic evolution may have affected trends and perturbations in global climate via changes in local organic carbon burial. Assessing the role of individual ocean basins in the global carbon-climate context requires a sound understanding of the processes that induced large-scale changes in carbon burial and the timing of these changes. Here we reconstruct the oceanographic evolution, and its links to organic carbon burial, in the Barremian to Albian South Atlantic and Southern Ocean basins, which may have acted as carbon sinks of global importance. Our reconstruction is based on combined seawater neodymium isotope and sedimentological records obtained from multiple deep sea drill sites and a new general circulation model. Deep water circulation within and between those basins was primarily controlled by the opening of the shallow Falkland Plateau Gateway (between ∼118 Ma and ∼113 Ma) and the deep Georgia Basin Gateway (by ∼110 Ma), for which we provide new age constraints based on biostratigraphic and carbon isotope data. The opening of these gateways was accompanied by local to basin-wide decreases in organic carbon burial, suggesting that ocean circulation affected the oxygenation state via changes in deep water ventilation. Although our data do not provide quantitative information on the impact of changes in regional organic carbon burial on the global carbon cycle, the synchronicity between the reduction of organic carbon burial in the South Atlantic basin and global warming during the Early Albian points to a strong causal relationship.

Description: Highlights • Nd isotope data reflect advection and dilution of Mediterranean Outflow Water on its way north in the Bay of Biscay. • Combined Hf and Nd isotopes are a sensitive indicator of inputs from land as well as long distance advection and mixing. • Nd isotope results of this and earlier studies demonstrate the temporally variable flow path of Mediterranean Sea Water. We present dissolved neodymium and hafnium concentrations and isotope compositions of surface and deep-water masses from the Bay of Biscay. Neodymium isotope signatures in surface waters of the Bay of Biscay are mostly dominated by local weathering inputs from the surrounding continental margin. Subsurface Eastern North Atlantic Central Water (ENACW) shows a distinct Nd isotope signature (εNd ≅ −12) at the southwestern-most station and is significantly diluted by mixing with more radiogenic waters or shifted by inputs of relatively radiogenic particulate Nd on its way north along the European margin. Furthermore, the Nd isotope data clearly show a declining fraction of Mediterranean Sea Water (MSW) at intermediate depths on its way north indicating that only 40% to 60% of MSW still present in the mixture at the Galician margin arrive at the stations further north in the Bay of Biscay. An interannual variability of the flow path of MSW is identified when comparing the results of the Nd isotope compositions and salinity data of this study with those of earlier studies from the area. In agreement with Nd isotope and concentration analyses the Hf isotope composition of MSW is set by large-scale inputs of terrigenous material into the Mediterranean as can be deduced from elevated Hf concentrations still observable at the Galician margin. Hf isotope signatures of all water masses of the Bay of Biscay, moreover, are overprinted by local weathering inputs and do not reflect water mass mixing. However, combined dissolved Nd and Hf isotopes serve as indicators of local weathering influences on signatures expected from long distance water mass mixing.

Description: Estuarine systems are of key importance for the riverine input of silicon (Si) to the ocean, which is a limiting factor of diatom productivity in coastal areas. This study presents a field dataset of surface dissolved Si isotopic compositions (30SiSi(OH)4) obtained in the estuaries of three of the world’s largest rivers, the Amazon (ARE), Yangtze (YRE), and Pearl (PRE), which cover different climate zones. While 30SiSi(OH)4 behaved conservatively in the YRE and PRE supporting a dominant control by water mass mixing, significantly increased 30SiSi(OH)4 signatures due to diatom utilization of Si(OH)4 were observed in the ARE and reflected a Si isotopic enrichment factor 30 of −1.0±0.4‰ (Rayleigh model) or −1.6±0.4‰ (steady state model). In addition, seasonal variability of Si isotope behavior in the YRE was observed by comparison to previous work and most likely resulted from changes in water residence time, temperature, and light level. Based on the 30 value obtained for the ARE, we estimate that the global average 30SiSi(OH)4 entering the ocean is 0.2-0.3‰ higher than that of the rivers due to Si retention in estuaries. This systematic modification of riverine Si isotopic compositions during estuarine mixing, as well as the seasonality of Si isotope dynamics in single estuaries, needs to be taken into account for better constraining the role of large river estuaries in the oceanic Si cycle.

Description: Highlights • Revised Nd implementation in the Bern3D model improves agreement with observations. • Dynamically consistent physical-biogeochemical framework including full Nd cycle. • Glacial Nd isotopes globally more radiogenic due to changed weathering input fluxes. • εNd behaved less conservatively during the glacial independent of the circulation. • Deglacial variability of the circulation best captured by εNd in the South Atlantic. Proxy reconstructions from deep ocean sediments have helped to shape our understanding of the role of the global overturning circulation in past climate change. Neodymium (Nd) isotopes have contributed to this knowledge, as a tracer of past bottom water provenance and mixing. Here, we extend the implementation of Nd isotopes in the physical-biogeochemical Bern3D model by revising a number of critical parameterizations, which result in an improved description of the marine Nd cycle. We exploit the dynamically consistent framework of the model, which allows us to assess the processes driving non-conservative Nd isotope behavior with a particular focus on the Last Glacial Maximum (LGM) and its substantially different climatic, oceanic, and biogeochemical boundary conditions. We show that the more radiogenic Nd isotopic compositions found throughout the glacial ocean can be explained by changes in the weathering input fluxes and do not require large reorganizations of the deep circulation. Our findings further highlight that the Nd isotopic composition of a water mass can not only be significantly affected by a benthic Nd flux, but also be modified by the vertical downward transport of Nd via reversible scavenging. While these non-conservative processes only have a limited impact in the modern ocean, they were substantially more pronounced during the LGM and mostly independent of the circulation state, with their contributions being non-linear, partially opposing, and spatially variable. During the transiently simulated deglaciation Nd isotope variations induced by major circulation weakenings and resumptions are found to be most pronounced in the South Atlantic, while they are increasingly muted towards the north. Hence, it emerges that the interpretation of authigenic Nd isotope records requires more spatially specific considerations of non-conservative processes in order to more reliably infer basin-scale ocean circulation and water mass mixing of the past.