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The Cretaceous opening of the Equatorial Atlantic gateway (EAG) is considered a driver of major changes in global oceanography, carbon cycling, and climate. However, the early stages of EAG opening are poorly understood. We present seawater Nd-isotope, bulk geochemical, and micropaleontological data from two South Atlantic drill cores that constrain the onset of shallow (2000 m) was enabled by at least ca. 100 Ma, as much as 10 m.y. earlier than previously estimated. In response to EAG opening, deep-water ventilation in the South Atlantic, North Atlantic, and Tethys basins intensified, thereby triggering basin-scale reductions in organic carbon burial. We propose that the consequent drop in carbon sequestration in concert with increased atmospheric CO2 fluxes from subduction zones acted as major amplifiers of global warming that culminated in peak greenhouse conditions during the mid-Cretaceous.

Ratios of (un)reactive iron species, authigenic molybdenum contents (Moauth), and molybdenum isotope compositions (δ98Moauth) in sedimentary rocks are geochemical proxies that are widely used to reconstruct past marine redox states, which have been calibrated in modern marine settings covering oxic to euxinic conditions. However, syn- and postdepositional processes can result in alterations and ambiguities of proxy-derived redox signals that can challenge the validity of paleoreconstructions. We present new data from modern organic-rich sediments of two oxygen minimum zone settings in the Gulf of California and the Peruvian margin. The results show that Mo is fully immobilized shortly after deposition by reaction with hydrogen sulfide (H2S) produced during organoclastic sulfate reduction. Thus, any H2S produced deeper in the sediment (e.g., by sulfate reduction coupled to anaerobic methane oxidation) leaves the initially deposited Mo concentrations and δ98Mo signatures unaltered, which supports the robustness of Mo-based redox proxies. In contrast, the Fe speciation data reveal continued pyritization due to constant exposure of Fe minerals to H2S. Importantly, both Fe bound to oxides and carbonates (highly reactive Fe) and also poorly reactive Fe (e.g., sheet silicates) undergo pyritization during early diagenesis. This process generates Fe-based proxy signatures that falsely imply ferruginous or euxinic conditions.

The late Miocene was a period of declining CO2 levels and extensive environmental changes, which likely had a large impact on monsoon strength as well as on the weathering and erosion intensity in the South Asian Monsoon domain. To improve our understanding of these feedback systems, detrital clays from the southern Bay of Bengal (International Ocean Discovery Program Site U1443) were analyzed for the radiogenic isotope compositions of Sr, Nd, and Pb to reconstruct changes in sediment provenance and weathering regime related to South Asian Monsoon rainfall from 9 to 5 Ma. The 100 kyr resolution late Miocene to earliest Pliocene record suggests overall low variability in the provenance of clays deposited on the Ninetyeast Ridge. However, at 7.3 Ma, Nd and Pb isotope compositions indicate a switch to an increased relative contribution from the Irrawaddy River (by ∼10%). This shift occurred during the global benthic δ13C decline, and we suggest that global cooling and increasing aridity resulted in an eastward shift of precipitation patterns leading to a more focused erosion of the Indo‐Burman Ranges. Sr isotope compositions were decoupled from Nd and Pb isotope signatures and became more radiogenic between 6 and 5 Ma. Grassland expansion generating thick, easily weatherable soils may have led to an environment supporting intense chemical weathering, which is likely responsible for the elevated detrital clay 87Sr/86Sr ratios during this time. This change in Sr isotope signatures may also have contributed to the late Miocene increase of the global seawater Sr isotope composition., Plain Language Summary: The South Asian or Indian monsoon affects the lives of billions. Through the erosion and weathering of rocks, the monsoon also has the potential to remove carbon dioxide from the atmosphere through increased weathering in the region including the Himalaya Mountains. The late Miocene, between 9 and 5 million years ago, was a period of global cooling and proliferation of grasslands in different regions including South Asia. Here, we examine the composition of clays formed by rock weathering during the late Miocene to determine their source region around the Bay of Bengal. The results suggest a generally stable mixture of sources with the strongest sources being regions with the highest monsoon rainfall today. We identify slight changes in the mixture of sources, which accompany a global change in carbon cycling, highlighting the role monsoon climate likely played in these changes. Toward the end of the Miocene, we identify a change in the Sr isotopes, which was not caused by source changes but by the strength of the rock weathering. This change has been observed in global records and it seems likely that it was driven by rock weathering in the South Asian Monsoon region., Highlights: Radiogenic isotope compositions of detrital clays from the Bay of Bengal indicate a generally stable provenance from 9 to 5 Ma. A step change in Nd and Pb isotope compositions at ∼7.3 Ma reflects a climatically driven eastward shift in precipitation patterns resulting in enhanced erosion of the Indo‐Burman Ranges. Elevated 87Sr/86Sr between 6 and 5 Ma was likely related to increased chemical weathering caused by thicker soils and by C4 plant expansion., DFG, ANR, IODP

The neodymium isotope composition ( ɛ Nd) of authigenic phases in marine sediment is widely used to reconstruct the origin and mixing of water masses of overlying seawater through time. However, at some locations in the modern ocean, the ɛ Nd of authigenic phases in surface sediment is not consistent with that of local seawater, raising concerns about its current interpretation as a paleotracer of water masses. To further investigate this question, we conducted a laboratory-based incubation experiment with a Mn-oxide phase placed at the sediment–water interface of multicores to assess the extent to which the authigenic phase records seawater ɛ Nd. Multicores were collected from the Strait of Georgia (SoG), which is a relatively deep coastal waterway with high sedimentation rates, oxygenated surface sediments, and active macrofauna, separating the mainland coast of British Columbia and Vancouver Island. Manganese oxide-coated XAD resin beads were placed at the sediment surface and the cores were incubated for 6 months in a tank filled with SoG seawater spiked with 150 Nd. While the ɛ Nd of the Mn-oxide coated resin (−4.0) was similar to that of SoG seawater used for the incubation (−3.7), the 150 Nd/ 144 Nd of the Mn-oxide phase measured after the incubation indicates that, under our experimental conditions, a minimum of 83% of the Nd associated with the Mn-oxide phase is not sourced from seawater, but from pore water. The 150 Nd/ 144 Nd ratio of the Mn-oxide resin is necessary to determine the predominant source of Nd to the resin because the ɛ Nd of SoG pore water (−3.9) is within analytical error of seawater (−3.7). Using field data and constraints from the Nd mass balance during the incubation, we conclude that the similarity of ɛ Nd in pore water and seawater in the SoG is fortuitous and not a result of a top-down or bottom-up control. Although the setting of our sediments is not directly comparable to open ocean locations, this study raises concerns about the use of ɛ Nd in paleocirculation studies, and points to the necessity of elucidating the factors controlling local lithogenic dissolution in pore waters as a prerequisite for the correct interpretation of ɛ Nd in the authigenic phases of marine sediments.

Highlights • Yangtze and Yellow River sediments can be distinguished with SrNd isotope. • Okinawa Trough (OT) sediments derived from the Yangtze River from 18.0 to 10.5 ka. • Yangtze and Yellow River contributed sediment to the OT from 10.5 to 7.0 ka. • Kuroshio Current control Taiwan sediment to the OT after 7.0 ka. • Yellow River sediment was transported to the OT by the coastal current in the last 10.5 ka. Abstract The Okinawa Trough (OT) is a large sink of sediments supplied by the East Asian continent. Identifying the provenance of the OT sediments is key to reconstructing the temporal and spatial variations of the terrigenous supply to this area and is important for understanding the impact of paleoclimatic and paleoceanographic variability on the sediment supply to this marginal sea over the late Quaternary. In this contribution, we show that radiogenic strontium (Sr) and neodymium (Nd) isotopes allow to efficiently distinguish Yellow and Yangtze/Taiwan River detrital sediments, and can be used to reconstruct distinct changes in the provenance of the detrital fraction of marine sediments from the middle and northern OT since the last deglaciation. The Sr and Nd isotope signatures are compared to those of the potential sediment sources, namely the Yellow and Yangtze Rivers, the Taiwan orogen, and volcanic material from the OT and nearby islands, and the relative contributions of these sources are reconstructed. The Sr and Nd isotope compositions of the detrital fraction in the two sediment cores recovered from the middle and northern OT show that the sediments mainly originated from the Yangtze River between 18 and 10.5 ka, which was caused by low sea level and a widely developed channel system on the continental shelf. During the period between 10.5 and 7.0 ka, the rising sea level resulted in elevated Yangtze and Yellow Rivers sediment input into the OT. Simultaneously, large-scale volcanic activity also contributed significant amounts of material to the OT. During the last 7.0 ka, besides important contributions from the Yellow River, the intensification of the Kuroshio Current resulted in increased delivery of sediment from Taiwan to the OT.

We present coupled cadmium (Cd) concentrations and Cd isotopic compositions (expressed as δ114Cd) in seawater profiles along the northeast-southwest GEOTRACES GA11 section in the tropical Atlantic Ocean. The GA11 section encompasses three contrasting regions including the Amazon River plume, the North African dust plume, and the Guinea Dome oxygen deficient zone (ODZ). Given the long oceanic residence time of Cd (104 to 105 yr), local inputs such as atmospheric and riverine sources are generally considered to be of little importance for the open ocean Cd budget, and the limited Cd isotope dataset available thus far has prevented any unambiguous conclusions on the importance of these processes. The GA11 section is ideally located for assessing the influence of external, natural and anthropogenic riverine and eolian inputs, as well as internal processes, on the Cd mass balance in the tropical Atlantic Ocean. As in previous Cd isotope studies, this dataset documents that both surface consumption–regeneration of micronutrients within the water column and deep water mass mixing exert the prime control on the cycling of Cd. However, we do observe some near-surface samples with lower-than-expected δ114Cd signatures along the western section of the transect. Surface waters sampled at the margin of the Amazon freshwater plume show no resolvable difference in [Cd] and δ114Cd compared to waters outside of the plume, suggesting that the Amazon River is not an important source of Cd to the open ocean. Although the eastern GA11 transect is directly downwind of the Saharan dust plume, atmospheric Cd deposition accounts for

Highlights • Icelandic input of radiogenic Nd essentially limited to coastal waters • Offshore bottom water Nd isotope signatures consistent with conservative mixing of intermediate and deep water masses • Decreased bottom water Nd concentrations likely reflect removal by particle scavenging Radiogenic neodymium (Nd) isotopes have been widely used as a proxy for tracing present and past water masses and ocean circulation, yet relatively few data exist for seawater from the important deep water formation area around Iceland. We have analyzed the dissolved seawater Nd isotope compositions (expressed as ƐNd) of 71 seawater samples, as well as Nd concentrations [Nd] of 38 seawater samples, collected at full water column profiles from 18 stations in the shelf area off the southern coast of Iceland. The goal of this work was to determine to what extent weathering inputs from Icelandic basalts, which are characterized by a distinctly radiogenic ƐNd signature within the North Atlantic, contribute to the Nd isotope and concentration signatures of water masses in the northern Iceland Basin. Radiogenic ƐNd values of up to −3.5 and elevated concentrations of up to 21 pmol/kg compared to nearby open ocean sites were found in surface waters at shallow sites closest to shore and to river mouths of Iceland. This documents partial dissolution of highly radiogenic basaltic particles, which are transported northwards by the coastal currents. A comparable signal is not observed, however, in offshore surface waters likely as a result of the advection of surface currents mainly directed onshore, thus isolating these sites from Icelandic weathering contributions. The dominance of Subpolar Mode Waters and Intermediate Water unaffected by Icelandic contributions in the offshore study area is supported by unradiogenic ƐNd signatures between −15 and −12. In agreement with hydrographic data, highly radiogenic bottom waters at one site on the Iceland-Faroe Ridge (ƐNd = −7.5) reveal the presence of almost pure Iceland Scotland Overflow Water (ISOW) near its formation site further to the east. In bottom waters of all deeper offshore sites, the combination of depleted Nd concentrations and similar ƐNd values (averaging at ≃−11.75 for the R/V Poseidon data and ≃−11 for the R/V Thalassa data) confirms the rapid entrainment of Atlantic mid-depth and deep waters into the overflow waters, which is accompanied by near bottom Nd removal via particle scavenging. Overall, our findings demonstrate that at present, apart from the radiogenic isotope signature of ISOW itself, the direct contribution of radiogenic Nd originating from weathering of Iceland basalts to the water column of the Iceland Basin is limited. This supports the reliable application of ƐNd values to trace changes in the mixing of open North Atlantic water masses (including ISOW).

Highlights • First comprehensive seawater Nd isotope and REE data set for the Barents Sea • Water masses traced with Nd isotopes, salinity and stable oxygen isotopes • No release of particulate REEs to the dissolved load except for cerium • Transformation of Atlantic Water accompanied by pronounced REE removal from the dissolved phase Abstract Nearly half the inflow of warm and saline Atlantic Water (AW) to the Arctic Ocean is substantially cooled and freshened in the Barents Sea, which is therefore considered a key region for water mass transformation in the Arctic Mediterranean. Numerous studies have focused on this transformation and the increasing influence of AW on Arctic climate and biodiversity, yet geochemical investigations of these processes have been scarce. Using the first comprehensive data set of the distributions of dissolved radiogenic neodymium (Nd) isotopes (expressed as ɛNd), rare earth elements (REE) and stable oxygen isotope (δ18O) compositions from this region we are able to constrain the transport and transformation of AW in the Barents Sea and to investigate which processes change the chemical composition of the water masses beyond what is expected from circulation and mixing. Inflowing AW and Norwegian Coastal Water (NCW) both exhibit distinctly unradiogenic ɛNd signatures of −12.4 and −14.5, respectively, whereas cold and dense Polar Water (PW) has considerably more radiogenic ɛNd signatures reaching up to −8.1. Locally formed Barents Sea Atlantic Water (BSAW) and Barents Sea Arctic Atlantic Water (BSAAW) are encountered in the northeastern Barents Sea and have intermediate ɛNd values resulting from admixture of PW containing small amounts of riverine freshwater from the Ob (

The development of the South Asian monsoon (SAM) and Himalaya‐Tibetan Plateau uplift were closely intertwined with some studies suggesting that uplift initiated the monsoon whereas others link tectonics with monsoon‐controlled exhumation. Silicate weathering controls atmospheric CO2 on geological timescales resulting in a large potential for monsoon strength and the Himalayan orogeny to influence global climate but detailed records of SAM‐induced weathering on million year (Myr) timescales are lacking. Here, we present radiogenic Sr, Nd, and Pb isotope compositions of clay minerals produced by silicate weathering and transported to the central Bay of Bengal. The radiogenic isotope data exhibit a relatively small range and demonstrate a remarkably consistent mixture of sources dominated by Himalayan rocks and the Indo‐Burman ranges, which consist of sediments derived from the Himalayas. This suggests that the spatial pattern of regional weathering, which today is highest in the regions of strongest monsoon rains, has persisted in a similar form for the last 27 Myrs. A pronounced increase in primary clay mineral abundance (from 9% to 22%) coincident with global cooling 13.9 Myrs ago points to a shift in the weathering regime given that the clay provenance did not change dramatically. Relatively weaker chemical weathering intensity during the mid and late Miocene cooling suggests increased aridity and changes in the large scale atmospheric circulation in the SAM domain. The establishment of the dry winter monsoon season during the mid and late Miocene may have caused this shift in the weathering regime and can reconcile much of the contrasting evidence for SAM initiation., Key Points: Relatively stable mixture of source rocks weathered to clays over the past 27 Myrs Pronounced increase in primary clay minerals occurred 13.9 Myrs ago Shift in weathering regime possibly result of winter monsoon dry season development

Tectonics and regional monsoon strength control weathering and erosion regimes of the watersheds feeding into the Bay of Bengal, which are important contributors to global climate evolution via carbon cycle feedbacks. The detailed mechanisms controlling the input of terrigenous clay to the Bay of Bengal on tectonic to orbital timescales are, however, not yet well understood. We produced orbital‐scale resolution geochemical records for International Ocean Discovery Program Site U1443 (southern Bay of Bengal) across five key climatic intervals of the middle to late Miocene (15.8–9.5 Ma). Our new radiogenic Sr, Nd, and Pb isotope time series of clays transported to the Ninetyeast Ridge suggest that the individual contributions from different erosional sources overall remained remarkably consistent during the Miocene despite major tectonic reorganizations in the Himalayas. On orbital timescales, however, high‐resolution data from the five investigated intervals show marked fluctuations of all three isotope systems. Interestingly, the variability was much higher within the Miocene Climatic Optimum (around 16–15 Ma) and across the major global cooling (~13.9–13.8 Ma) until ~13.5 Ma, than during younger time intervals. This change is attributed to a major restriction on the supply of High Himalayan erosion products due to migration of the peak precipitation area toward the frontal domains of the Himalayas and the Indo‐Burman Ranges. The transient excursions of the radiogenic isotope signals on orbital timescales most likely reflect climatically driven shifts in monsoon strength., Key Points: A consistent mix of clay sources contributed to the Bay of Bengal throughout the middle to late Miocene A marked change in detrital Sr, Nd, and Pb isotope variability at 13.5 Ma was related to Miocene global cooling Transient orbital‐scale fluctuations in clay source most likely reflect changes in monsoon intensity, Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/501100001659

The sluggish water mass transport in the deeper North Pacific Ocean complicates the assessment of formation, spreading and mixing of surface, intermediate and deep-water masses based on standard hydrographic parameters alone. Geochemical tracers sensitive to water mass provenance and mixing allow to better characterize the origin and fate of the prevailing water masses. Here, we present dissolved neodymium (Nd) isotope compositions (εNd) and concentrations ([Nd]) obtained along a longitudinal transect at ∼180°E from ∼7°S to ∼50°N. The strongest contrast in Nd isotope signatures is observed in equatorial regions between surface waters (εNd ∼0 at 4.5°N) and Lower Circumpolar Deep Water (LCDW) prevailing at 4500 m depth (εNd = −6.7 at 7.2°N). The Nd isotope compositions of equatorial surface and subsurface waters are strongly influenced by regional inputs from the volcanic rocks surrounding the Pacific, which facilitates the identification of the source regions of these waters and seasonal changes in their advection along the equator. Highly radiogenic weathering inputs from Papua-New-Guinea control the εNd signature of the equatorial surface waters and strongly alter the εNd signal of Antarctic Intermediate Water (AAIW) by sea water-particle interactions leading to an εNd shift from −5.3 to −1.7 and an increase in [Nd] from 8.5 to 11.0 pmol/kg between 7°S and 15°N. Further north in the open North Pacific, mixing calculations based on εNd, [Nd] and salinity suggest that this modification of the AAIW composition has a strong impact on intermediate water εNd signatures of the entire region allowing for improved identification of the formation regions and pathways of North Pacific Intermediate Water (NPIW). The deep-water Nd isotope signatures indicate a southern Pacific origin and subsequent changes along its trajectory resulting from a combination of water mass mixing, vertical processes and Nd release from seafloor sediments, which precludes Nd isotopes as quantitative tracers of deep-water mass mixing. Moreover, comparison with previously reported data indicates that the Nd isotope signatures and concentrations below 100 m depth essentially remained stable over the past decades, which suggests constant impacts of water mass advection and mixing as well as of non-conservative vertical exchange and bottom release.

North African greening phases, during which large rivers ran through the Sahara Desert, occurred repeatedly during the Quaternary and are regarded as key periods for the development of past human populations. However, the timing and mechanisms responsible for the reactivation of the presently dormant fluvial systems remain highly uncertain. Here we present hydroclimate changes over the past 160,000 years, reconstructed from analyses of the provenance of terrestrial sediments in a marine sediment record from the Gulf of Sirte (offshore Libya). By combining high-resolution proxy data with transient Earth system model simulations, we are able to identify the various drivers that led to the observed shifts in hydroclimate and landscapes. We show that river runoff occurred during warm interglacial phases of Marine Isotope Stages 1 and 5 due to precession-forced enhancements in the summer and autumn rainfall over the entire watershed, which fed presently dry river systems and intermittent coastal streams. In contrast, shorter-lasting and less-intense humid events during glacial Marine Isotope Stages 3 and 4 were related to autumn and winter precipitation over the Libyan coastal regions driven by Mediterranean storms. Our results reveal large shifts in hydroclimate environments during the last glacial cycle, which probably exerted a strong evolutionary and structural control on past human populations, potentially pacing their dispersal across northern Africa. The presence of large rivers in North Africa critical for Quaternary human migrations were controlled by a combination of orbital forcing and Mediterranean storminess, according to terrestrial proxy records from a marine core off Libya integrated with paleoclimate modelling.

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.

Increased carbon sequestration in the ocean subsurface is commonly assumed to have been one of the main causes responsible for lower glacial atmospheric CO2 concentrations. This carbon must have been stored away from the atmosphere for thousands of years, yet the water mass structure accommodating such increased carbon storage continues to be debated. Here we present new sediment derived bottom water neodymium isotope data that allow fingerprinting of water masses and their mixtures and provide a more complete picture of the Atlantic overturning circulation geometry during the Last Glacial Maximums. These results suggest that the vertical and meridional structure of the Atlantic deep water mass distribution only experienced minor changes since the last ice age. In particular, we find no compelling evidence supporting glacial southern sourced water substantially expanding to shallower depths and farther into the northern hemisphere than today, which has been inferred from stable carbon isotope reconstructions. We argue that depleted δ13C values observed in the deep Northwest Atlantic do not necessarily indicate the presence of southern sourced water. Instead, these values may represent a northern sourced water mass with lower than modern preformed δ13C values that were further modified downstream by increased sequestration of remineralized carbon, facilitated by a more sluggish glacial deep circulation. If proven to be correct, the glacial water mass structure inferred from Nd isotopes has profound implications on our understanding of the deep ocean carbon storage during the Last Glacial Maximum.

The lifetime and thickness of Arctic sea ice have markedly decreased in the recent past. This affects Arctic marine ecosystems and the biological pump, given that sea ice acts as platform and transport medium of marine and atmospheric nutrients. At the same time sea ice reduces light penetration to the Arctic Ocean and restricts ocean/atmosphere exchange. In order to understand the ongoing changes and their implications, reconstructions of source regions and drift trajectories of Arctic sea ice are imperative. Automated ice tracking approaches based on satellite-derived sea-ice motion products (e.g. ICETrack) currently perform well in dense ice fields, but provide limited information at the ice edge or in poorly ice-covered areas. Radiogenic neodymium (Nd) isotopes (εNd) have the potential to serve as a chemical tracer of sea-ice provenance and thus may provide information beyond what can be expected from satellite-based assessments. This potential results from pronounced εNd differences between the distinct marine and riverine sources, which feed the surface waters of the different sea-ice formation regions. We present the first dissolved (< 0.45 µm) Nd isotope and concentration data obtained from optically clean Arctic first- and multi-year sea ice (ice cores) collected from different ice floes across the Fram Strait during the RV POLARSTERN cruise PS85 in 2014. Our data confirm the preservation of the seawater εNdsignatures in sea ice despite low Nd concentrations (on average ~ 6 pmol/kg) resulting from efficient brine rejection. The large range in εNd signatures (~ -10 to -30) mirrors that of surface waters in various parts of the Arctic Ocean, indicating that differences between ice floes but also between various sections in an individual ice core reflect the origin and evolution of the sea ice over time. Most ice cores have εNd signatures of around -10, suggesting that the sea ice was formed in well-mixed waters in the central Arctic Ocean and transported directly to the Fram Strait via the Transpolar Drift. Some ice cores, however, also revealed highly unradiogenic signatures (εNd < ~ -15) in their youngest (bottom) sections, which we attribute to incorporation of meltwater from Greenland into newly grown sea ice layers. Our new approach facilitates the reconstruction of the origin and spatiotemporal evolution of isolated sea-ice floes in the future Arctic.

Deep water formation in the North Atlantic represents an integral link between the atmosphere, cryosphere, and the deep ocean: heat loss from warm surface waters supplies moisture to the high latitudes and their subsequent sinking ventilates the deep ocean and sequesters greenhouse gases from the atmosphere. This moisture supply supported the formation of immense ice sheets in the region during the last glacial, which in turn affected climate. While many studies have improved our understanding of these processes for past glacials, a comprehensive picture including the significance and variation of deep water export from the Nordic Seas is still missing. Furthermore, recent observations suggested the export of a previously unknown bottom water mass from the glacial subpolar North Atlantic.In this study we investigate the distribution and sourcing of water masses in the subpolar North Atlantic since MIS3 with the help of authigenic Nd isotopes. This method benefits from the large heterogeneity in Nd isotopic compositions of source rocks in this region, but the post-depositional dissolution of detritus within the sediments can also impede interpretations of individual records. We thus compare several Nd isotope records from the subpolar North Atlantic and Nordic Seas in order to define distinct deep water mass end members and estimate their prevalence and mixing in the subpolar North Atlantic during the last 30 ka. Our observations suggest that Nordic Seas deep water overflowing the Greenland-Scotland Ridge during MIS2 reached into the deep subpolar North Atlantic. Furthermore, its spatial distribution implies that overflow across Denmark Strait into the Irminger Basin was more pronounced than overflow into the Iceland Basin further south. The hydrographic configuration during the Last Glacial Maximum thus appears to have been more complex and more similar to today than previously thought.

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.

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.

The Asian summer monsoon affects the lives of billions of people. With the aim of identifying geochemical tracers for the monsoon related freshwater input from the major rivers draining into the Bay of Bengal and Andaman Sea we have taken surface seawater samples from various locations up and down the Andaman Islands during 2011. Importantly, in some locations samples have been taken in March, July and November, covering most of a seasonal cycle and different monsoon phases. Samples were collected from the side of small wooden boats or while swimming and were filtered within a few hours at 0.45 or 0.22 microns using the vacuum produced by a water jet or a hand operated peristaltic pump. Filtered and unfiltered samples were acidified to < pH 2 and analysed for Y and the REEs with an automated online preconcentration ICP-MS technique [1]. The local input of REEs from streams and sediment rich areas such as mangrove environments is clearly identified by middle REE enrichments in the shale normalised patterns of some samples. These middle REE bulges accompany large increases in dissolved REE concentrations at some locations, especially for the July samples obtained during the peak monsoon season with frequent storms. Y/Ho fractionation aslo occurs during the local input of dissolved REEs with affected samples having lower Y/Ho ratios. Conversly, some samples, in particular those taken after heavy rainfall in March, show strong REE scavenging accompanied by the prefferential removal of dissolved light REEs and higher Y/Ho ratios. The time series at a location away from local input sources shows remarkably similar REE patterns and concentraions in March and July. Then in October-November, following the peak in monsoon river discharge, the dissolved REE concentration increases by almost a factor of 2. The notable exception to this seasonal pattern is the Ce anomally which is around 0.3 in March and November but 0.6 in July, implying less oxidative removal of Ce(IV) during the peak summer monsoon rains. With the exception of elevated dissolved Ce concentrations, the North Pacific Deep Water normalised REE patterns are similar to those reported for offshore samples from the Bay of Bengal and Andaman Sea [2]. These seawater normalised patterns are distinctive having a middle REE enriched arc with similar light and heavy REE values suggesting the input from large rivers in the region is traceable using seawater REE chemistry. [1] Hathorne et al. (2012), Online preconcentration ICP-MS analysis of rare earth elements in seawater, Geochem. Geophys. Geosyst., 13, Q01020, doi:10.1029/2011GC003907. [2] Amakawa et al. (2000), Geochim. Cosmochim. Acta 64, 1715-1727.

The cause of rapid hydrological changes in the tropical West Pacific during the last deglaciation remains controversial. In order to test whether these changes were triggered by abrupt climate change events in the North Atlantic Ocean, variations in precipitation during the last deglaciation (18–10 ka) were extracted from proxy records of chemical weathering and terrigenous input in the western Philippine Sea (WPS). The evolution of chemical weathering and terrigenous input since 27 ka was reconstructed using the chemical index of alteration (CIA), elemental ratios (K/Al, TOC/TN and Ti/Ca), δ13Corg, terrigenous fraction abundance and flux data from International Marine Global Change Study Program (IMAGES) core MD06-3054 collected on the upper continental slope of eastern Luzon (northern Philippines). Sediment deposited during the Last Glacial Maximum (LGM) shows weathering equal to or slightly greater than Holocene sediment in the WPS. This unusual state of chemical weathering, which is inconsistent with lower air temperatures and decreased precipitation in Luzon during the LGM, may be due to reworking of poorly consolidated sediments on the eastern Luzon continental shelf during the LGM sea-level lowstand. Rapid changes in chemical weathering, characterized by higher intensity during the Heinrich event 1 (H1) and Younger Dryas (YD) and lower intensity during the Bolling-Allerod (B/A), were linked to rapid variations in precipitation in the WPS during the last deglaciation. The higher terrigenous inputs during the LGM relative to those of the Holocene were controlled by sea-level changes rather than precipitation. The terrigenous inputs show a long-term decline during the last deglaciation, punctuated by brief spikes during the H1 and YD related to sea-level rises and rapid precipitation changes in the WPS, respectively. The proxy records of chemical weathering and terrigenous input from eastern Luzon suggest high rainfall during the H1 and YD events, consistent with inferred rainfall patterns based on Fe/Ca records from offshore Mindanao. Rapid precipitation changes in the WPS did not coincide with migrations of the Intertropical Convergence Zone (ITCZ) but, rather, were related to state shifts of the El Nino-Southern Oscillation (ENSO) during the last deglaciation. Based on proxy records and modeling results, we argue that the Atlantic meridional overturning circulation (AMOC) controlled rapid precipitation changes in the tropical West Pacific through zonal shifts of ENSO or meridional migration of the ITCZ during the last deglaciation. Our findings highlight the dominant role of the North Atlantic Ocean in the tropical hydrologic cycle during the last deglaciation.

Marine neodymium (Nd) isotope and rare earth element (REE) compositions are valuable tracers for present and past ocean circulation and continental inputs. Yet their supply via high latitude estuaries is largely unknown. Here we present a comprehensive dissolved Nd isotope (expressed as eNd values) and REE data set together with seawater stable oxygen isotope ( δ 18 O) compositions of samples from the Laptev Sea recovered in two Arctic summers and one winter. The Laptev Sea is a shallow Siberian Shelf sea characterized by extensive river-runoff, sea-ice production and ice transport into the Arctic Ocean. The large variability in eNd (−6 to −17), REE concentrations (16 to 600 pmol/kg for Nd) and REE patterns is controlled by freshwater supply from distinct riverine sources and open ocean Arctic Atlantic Water. Strikingly and contrary to expectations, except for cerium no evidence for significant release of REEs from particulate phases is found, which is attributed to low amounts of suspended particulate matter and high dissolved organic carbon concentrations present in the contributing rivers. Essentially all shelf waters are depleted in light (L)REEs, while the distribution of the heavy REEs shows a deficiency at the surface and a pronounced excess in the bottom layer. This distribution is consistent with REE removal through coagulation of riverine nanoparticles and colloids starting at salinities near 10 and resulting in a drop of all REE concentrations by ∼30%. With increasing salinity preferential LREE removal is observable reaching ∼75% for Nd at a salinity of 34. Although the delayed onset of dissolved REE removal contrasts with most previous observations from other estuarine environments, it agrees remarkably well with results from recent experiments simulating estuarine mixing of seawater with organic-rich river waters. In addition, melting and formation of sea ice leads to further REE depletion at the surface and strong REE enrichment near the shelf bottom as a function of ice melting and brine transfer, respectively. The ice-related processes significantly affect the distribution of dissolved REEs in high-latitude estuaries and likely also similarly contribute to the redistribution of other dissolved seawater constituents.

The distribution of dissolved rare earth elements (REEs) and neodymium isotopes (eNd) in the open ocean traces water mass mixing and provides information on lithogenic inputs to the source regions of the water masses. However, the processes influencing the REE budget at the ocean margins, in particular source and sink mechanisms, are not yet well quantified. In this study the first dissolved REE concentrations and Nd isotope compositions of seawater from the Panama Basin (RV Meteor cruise M90) in the Eastern Equatorial Pacific (EEP) are presented. The EEP is characterized by one of the world's largest oxygen minimum zones (OMZs). It is dominated by high particle fluxes that are expected to enhance the removal of REEs from the water column by scavenging. The measured REE concentrations peak at the surface indicating high lithogenic input, which is supported by shale-normalized REE patterns in surface waters and highly radiogenic eNd signatures ranging between +1.4 and +4.3, the latter value constituting the most radiogenic value measured for seawater to date. In contrast, intermediate and deep water REE concentrations are low compared to other Pacific Basins and suggest enhanced removal via scavenging associated with high particle fluxes. The eNd signatures of intermediate and deep waters are less radiogenic than surface waters ranging between −1.4 and +1.3 but significantly more radiogenic than source water masses in the EEP. The eNd signatures consequently do not reflect mixing of intermediate and deep water masses entering the Panama Basin but can only be explained by lithogenic inputs originating from source rocks with highly radiogenic Nd isotope signatures such as the Central American Volcanic Arc ( e Nd = + 3 to +10). Our data demonstrate significant surface input via continental particles, which are partially dissolved in the water column and thereby release REEs and particularly radiogenic Nd isotope signatures to the subsurface ocean. Data obtained from a re-occupied station in the southern Panama Basin for the first time shows that these processes can partially reset water mass Nd isotope and REE signatures of the entire water column proximal to continental sources on time scales of a few years.

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 µg g−1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the ‘anomalously’ high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

The ultimate, possibly geodynamic control and potential impact of changes in circulation activity and salt discharge of Mediterranean outflow waters (MOW) on Atlantic meridional overturning circulation have formed long-standing objectives in paleoceanography. Late Pliocene changes in the distal advection of MOW were reconstructed on orbital timescales for northeast Atlantic DSDP/ODP sites 548 and 982 off Brittany and on Rockall Plateau, supplemented by a proximal record from Site U1389 west off Gibraltar, and compared to Western Mediterranean surface and deep-water records of Alboran Sea Site 978. From ~3.43 to 3.3 Ma, MOW temperatures and salinities form a prominent rise by 2–4 °C and ~3 psu, induced by a preceding and coeval rise in sea surface and deep-water salinity and increased summer aridity in the Mediterranean Sea. We speculate that these changes triggered an increased MOW flow and were ultimately induced by a persistent 2.5 °C cooling of Indonesian Through-Flow waters. The temperature drop resulted from the northward drift of Australia that crossed a threshold value near 3.6–3.3 Ma and led to a large-scale cooling of the eastern subtropical Indian Ocean and in turn, to a reduction of African monsoon rains. Vice versa, we show that the distinct rise in Mediterranean salt export after ~3.4 Ma induced a unique long-term rise in the formation of Upper North Atlantic Deep Water, that followed with a phase lag of ~100 ky. In summary, we present evidence for an interhemispheric teleconnection of processes in the Indonesian Gateways, the Mediterranean and Labrador Seas, jointly affecting Pliocene climate.

Highlights • First high-resolution Cdw-record from Caribbean intermediate waters. • Rapid nutrient enrichment during HS1 and YD. • Tropical N-Atlantic AAIW nutrient content controlled by Southern Ocean. • Enhanced AAIW nutrient content likely fed low to high latitude productivity. • Dampening of the deglacial global CO2 rise by AAIW nutrient enrichment. As part of the return flow of the Atlantic overturning circulation, Antarctic Intermediate Water (AAIW) redistributes heat, salt, CO2and nutrients from the Southern Ocean to the tropical Atlantic and thus plays a key role in ocean–atmosphere exchange. It feeds (sub)tropical upwelling linking high and low latitude ocean biogeochemistry but the dynamics of AAIW during the last deglaciation remain poorly constrained. We present new multi-decadal benthic foraminiferal Cd/Ca and stable carbon isotope (δ13C) records from tropical W-Atlantic sediment cores indicating abrupt deglacial nutrient enrichment of AAIW as a consequence of enhanced deglacial Southern Ocean upwelling intensity. This is the first clear evidence from the intermediate depth tropical W-Atlantic that the deglacial reconnection of shallow and deep Atlantic overturning cells effectively altered the AAIW nutrient budget and its geochemical signature. The rapid nutrient injection via AAIW likely fed temporary low latitude productivity, thereby dampening the deglacial rise of atmospheric CO2.

Combined seawater radiogenic hafnium (Hf) and neodymium (Nd) isotope compositions were extracted from bulk sediment leachates and foraminifera of Site 1088, ODP Leg 177, 2082 m water depth on the Agulhas Ridge. The new data provide a continuous reconstruction of long and short-term changes in ocean circulation and continental weathering inputs since the Mid-Miocene. Due to its intermediate water depth the sediments of this core sensitively recorded changes in admixture of North Atlantic Deep Water (NADW) to the Antarctic Circumpolar Current (ACC) as a function of the strength of the Atlantic Meridional Overturning Circulation (AMOC). Nd isotope compositions (eNd) range from -7 to -11 with glacial values generally 1 to 3 units more radiogenic than during the interglacials of the Quaternary. The data reveal episodes of significantly increased AMOC strength during late Miocene and Pliocene warm periods whereas peak radiogenic eNd values mark a strongly diminished AMOC during the major intensification of Northern Hemisphere Glaciation near 2.8 Ma and in the Pleistocene after 1.5 Ma. In contrast, the Hf isotope compositions (eHf) show an essentially continuous evolution from highly radiogenic values of up to +11 during the Miocene to less radiogenic present day values (+2 to +4) during the late Quaternary. The data document a long-term transition in dominant weathering inputs, where inputs from the South America are replaced by those from Southern Africa. Moreover, radiogenic peaks provide evidence for the supply of radiogenic Hf originating from Patagonian rocks to the Atlantic sector of the Southern Ocean via dust inputs.

The Labrador Sea is one of the key areas for deep water formation driving the Atlantic thermohaline circulation and thus plays an important role in Northern Hemisphere climatic fluctuations. In order to better constrain the overturning processes and the origins of the distinct water masses, combined dissolved Hf–Nd isotopic compositions and rare earth element (REE) distribution patterns were obtained from four water depth profiles along a section across the Labrador Sea. These were complemented by one surface sample off the southern tip of Greenland, three shallow water samples off the coast of Newfoundland, and two deep water samples off Nova Scotia. Although light REEs are markedly enriched in the surface waters off the coast of Newfoundland compared to north Atlantic waters, the REE concentration profiles are essentially invariant throughout the water column across the Labrador Sea. The hafnium concentrations of surface waters exhibit a narrow range between 0.6 and 1 pmol/kg but are not significantly higher than at depth. Neodymium isotope signatures (ɛNd) vary from unradiogenic values between −16.8 and −14.9 at the surface to more radiogenic values near −11.0 at the bottom of the Labrador Sea mainly reflecting the advection of the Denmark Strait Overflow Water and North East Atlantic Deep Water, the signatures of which are influenced by weathering contributions from Icelandic basalts. Unlike Nd, water column radiogenic Hf isotope signatures (ɛHf) are more variable representing diverse weathering inputs from the surrounding landmasses. The least radiogenic seawater ɛHf signatures (up to −11.7) are found in surface waters close to Greenland and near the Canadian margin. This reflects the influence of recirculating Irminger Current Waters, which are affected by highly unradiogenic inputs from Greenland. A three to four ɛHf unit difference is observed between Denmark Strait Overflow Water (ɛHf ∼ −4) and North East Atlantic Deep Water (ɛHf ∼ −0.1), although their source waters have essentially the same ɛNd signature. This most likely reflects different weathering signals of hafnium delivered to Denmark Strait Overflow Water and North East Atlantic Deep Water (incongruent weathering of old rocks from Greenland versus basaltic rocks from Iceland). In addition, the ɛHf data resolve two layers within the main body of Labrador Sea Water not visible in the ɛNd distribution, which are shallow Labrador Sea Water (ɛHf ∼ −2) and deep Labrador Sea Water (ɛHf ∼ −4.5). The latter layer was formed between the late 1980’s and mid 1990’s during the last cold state of the Labrador Sea and underwent substantial modification since its formation through the admixture of Irminger Water, Iceland Slope Water and North East Atlantic Deep Water, which is reflected in its less radiogenic ɛHf signature. The overall behavior of Hf in the water column suggests its higher sensitivity to local changes in weathering inputs on annual to decadal timescales. Although application of Hf isotopes as a tracer for global water mass mixing is complicated by their susceptibility to incongruent weathering inputs they are a promising tracer of local processes in restricted basins such as the Labrador Sea.

The formation of the Antarctic Circumpolar Current (ACC) is critical for the evolution of the global climate, but the timing of its onset is not well constrained. Here, we present new seismic evidence of widespread Late Eocene to Oligocene marine diagenetic chert in sedimentary drift deposits east of New Zealand indicating prolonged periods of blooms of siliceous microorganisms starting ~36 million years ago (Ma). These major blooms reflect the initiation of the arrival and upwelling of northern-sourced, nutrient-rich deep equatorial Pacific waters at the high latitudes of the South Pacific. We show that this change in circulation was linked to the initiation of a proto-ACC, which occurred ~6 Ma earlier than the currently estimated onset of the ACC at 30 Ma. We propose that the associated increased primary productivity and carbon burial facilitated atmospheric carbon dioxide reduction contributing to the expansion of Antarctic Ice Sheet at the Eocene-Oligocene Transition.

Dissolved neodymium (Nd) and its radiogenic isotope composition (143Nd/144Nd, expressed as eNd) belong to the key parameters of the international GEOTRACES program, which aims to investigate the processes controlling the distribution of trace elements and their isotopes in the global ocean. We present Nd isotope and concentration ([Nd]) data from eleven full depth water column profiles from the eastern (sub)tropical Atlantic Ocean between 2°N and 29°N and from the Romanche Fracture Zone sampled during Meteor cruise M81/1 (GEOTRACES cruise GA11) in February/March 2010. The eNd signatures range from −12.9 in upper North Atlantic Deep Water (UNADW) at the equator to −8.1 in the mixed layer near the Canary Islands. Nd concentrations range from 11.9 pmol/kg observed within the Equatorial Undercurrent to 40.2 pmol/kg in Antarctic Bottom Water (AABW) in the Romanche Fracture Zone. Large variations in surface water Nd isotope compositions (−12.7 ≤ eNd ≤ −8.1) and concentrations (15.7 pmol/kg ≤ [Nd] ≤ 27.7 pmol/kg) are caused by partial dissolution of Saharan dust particles between 2°N and 13°N and volcanic island weathering (Canaries) between 25°N and 29°N. In contrast to dust inputs, which predominantly affect the Nd concentrations and isotope compositions of surface waters and underlying South Atlantic Central Water (SACW), contributions originating from the Canary Islands affect the Nd isotope composition of the entire surrounding water column without significantly altering Nd concentrations, thus confirming the concept of boundary exchange in its strictest sense. The results confirm that the composition of lower North Atlantic Deep Water (LNADW, eNd = −12.1) in the abyssal plains of the eastern North Atlantic is exclusively set by the mixing ratio of LNADW and Antarctic Bottom Water (AABW). Upper North Atlantic Deep Water (UNADW), in contrast, is characterized by eNd signatures between −12.7 and − 12.0 between 2°N and 10°N, whereas further north it is clearly affected by admixture of Mediterranean Water (MW) and radiogenic inputs from the Canary Islands and likely also the Cape Verde Islands. This article is part of a special issue entitled: “Cycles of trace elements and isotopes in the ocean – GEOTRACES and beyond” - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. Gonzalez.

Over the past decades, observations have confirmed decreasing oxygen levels and shoaling of oxygen minimum zones (OMZs) in the tropical oceans. Such changes impact the biogeochemical cycling of micronutrients such as Cd, but the potential consequences are only poorly constrained. Here, we present seawater Cd concentrations and isotope compositions for 12 depth profiles at coastal, nearshore and offshore stations from 4°S to 14°S in the eastern tropical South Pacific, where one of the world's strongest OMZs prevails. The depth profiles of Cd isotopes display high δ 114 / 110 Cd at the surface and decreasing δ 114 / 110 Cd with increasing water depth, consistent with preferential utilization of lighter Cd isotopes during biological uptake in the euphotic zone and subsequent remineralization of the sinking biomass. In the surface and subsurface ocean, seawater displays similar δ 114 / 110 Cd signatures of 0.47 ± 0.23‰ to 0.82 ± 0.05‰ across the entire eastern tropical South Pacific despite highly variable Cd concentrations between 0.01 and 0.84 nmol/kg. This observation, best explained by an open system steady-state fractionation model, contrasts with previous studies of the South Atlantic and South Pacific Oceans, where only Cd-deficient waters have a relatively constant Cd isotope signature. For the subsurface to about 500 m depth, the variability of seawater Cd isotope compositions can be modeled by mixing of remineralized Cd with subsurface water from the base of the mixed layer. In the intermediate and deep eastern tropical South Pacific (>500 m), seawater [Cd] and δ 114 / 110 Cd appear to follow the distribution and mixing of major water masses. We identified modified AAIW of the ETSP to be more enriched in [Cd] than AAIW from the source region, whilst both water masses have similar δ 114 / 110 Cd . A mass balance estimate thus constrains a δ 114 / 110 Cd of between 0.38‰ and 0.56‰ for the accumulated remineralized Cd in the ETSP. Nearly all samples show a tight coupling of Cd and PO4 concentrations, whereby surface and deeper waters define two distinct linear trends. However, seawater at a coastal station located within a pronounced plume of H2S, is depleted in [Cd] and features significantly higher δ 114 / 110 Cd . This signature is attributed to the formation of authigenic CdS with preferential incorporation of lighter Cd isotopes. The process follows a Rayleigh fractionation model with a fractionation factor of α 114 / 110 Cd seawater-CdS = 1.00029. Further deviations from the deep Cd–PO4 trend were observed for samples with O2

The Tethys Ocean was compartmentalized into the Mediterranean Sea and Indian Ocean during the early Miocene, yet the exact nature and timing of this disconnection are not well understood. Here we present two new neodymium isotope records from isolated carbonate platforms on both sides of the closing seaway, Malta (outcrop sampling) and the Maldives (IODP Site U1468), to constrain the evolution of past water mass exchange between the present day Mediterranean Sea and Indian Ocean via the Mesopotamian Seaway. Combining these data with box modeling results indicates that water mass exchange was reduced by ~90% in a first step at ca. 20 Ma. The terminal closure of the seaway then coincided with the sea level drop caused by the onset of permanent glaciation of Antarctica at ca. 13.8 Ma. The termination of meridional water mass exchange through the Tethyan Seaway resulted in a global reorganization of currents, paved the way to the development of upwelling in the Arabian Sea and possibly led to a strengthening of South Asian Monsoon., peer-reviewed

The neodymium isotope proxy has become a valuable tool for the reconstruction of past ocean water mass provenance and mixing. For its accurate application, knowledge about the origin and preservation of Nd in sedimentary archives is crucial. Recently, concerns have emerged regarding the applicability of neodymium isotopes as a conservative palaeo water mass tracer, given potential Nd fluxes from sediments into bottom waters (Abbott et al., 2015a) and inferred relabelling of ocean waters by settling detrital material (Roberts and Piotrowski, 2015). Consequently, a decoupling of water mass provenance and proxy variations may arise. We investigate the mobility of Nd around extreme detrital sedimentation events such as glacial ice rafting pulses and turbidite deposition in the Northeast Atlantic. The constructed records from sediment leachates span extreme Nd isotope variations including volcanic (eNd ∼ 0) and Laurentian (eNd ∼ −27) sources. We find that Nd was released into pore waters from reactive detritus inside some detrital layers during early diagenesis, thereby overprinting any archived bottom water Nd signature and precluding the reconstruction of past water mass provenance during the affected time intervals. However, we do not observe any definite indication of diffusive vertical migration of Nd into adjacent layers. Furthermore, bottom water Nd isotope signatures were not modified to a measurable degree by any potential benthic flux of Nd during the deposition of these detrital sediment layers. Consequently, the Nd isotope composition of the pelagic glacial Northeast Atlantic water masses were resilient to such episodic large detrital fluxes. Apart from extreme local sedimentation events, we confirm the presence of detritally overprinted deep waters north of 47°N during the peak glacial from comparison of Northeast Atlantic depth transects. We furthermore suggest that the sensitivity of deep waters to this overprinting effect increased during periods of reduced Atlantic Meridional Overturning Circulation and elevated ice rafting. Overall, our study demonstrates that a thorough evaluation of the proportion of Nd originating from physical water mass advection versus in situ chemical inputs is crucial for the reliable application of Nd isotopes as a water mass tracer.

During the Late Cretaceous and early Cenozoic the Earth experienced prolonged climatic cooling most likely caused by decreasing volcanic activity and atmospheric CO2 levels. However, the causes and mechanisms of subsequent major global warming culminating in the late Paleocene to Eocene greenhouse climate remain enigmatic. We present deep and intermediate water Nd-isotope records from the North and South Atlantic to decipher the control of the opening Atlantic Ocean on ocean circulation and its linkages to the evolution of global climate. The marked convergence of Nd-isotope signatures 59 million years ago indicates a major intensification of deep-water exchange between the North and South Atlantic, which coincided with the turning point of deep-water temperatures towards early Paleogene warming. We propose that this intensification of Atlantic overturning circulation in concert with increased atmospheric CO2 from continental rifting marked a climatic tipping point contributing to a more efficient distribution of heat over the planet., Ocean circulation likely played a major role in past episodes of global warming. Here the authors show that converging neodymium isotope values indicate intensification of the Atlantic overturning circulation at 59 million years ago, which may have contributed to a more efficient distribution of heat over the planet.

Antarctic Intermediate Water (AAIW) is an important conduit for nutrients to reach the nutrient‐poor low‐latitude ocean areas. In the Atlantic, it forms part of the return path of the Atlantic Meridional Overturning Circulation (AMOC). Despite the importance of AAIW, little is known about variations in its composition and signature during the prominent AMOC and climate changes of the last deglaciation. Here, we reconstruct benthic foraminiferal Mg/Ca‐based intermediate water temperatures (IWTMg/Ca) and intermediate water neodymium (Nd) isotope compositions at sub‐millennial resolution from unique sediment cores located at the northern tip of modern AAIW extent in the tropical W‐Atlantic (850 and 1018 m water depth). Our data indicate a pronounced warming of AAIW in the tropical W‐Atlantic during Heinrich Stadial 1 (HS1) and the Younger Dryas (YD). We argue that these warming events were induced by major AMOC perturbations resulting in the pronounced accumulation of heat in the surface Southern Ocean. Combined with published results, our data suggest the subsequent uptake of Southern Ocean heat by AAIW and its rapid northward transfer to the tropical W‐Atlantic. Hence, the rapid deglacial northern climate perturbations directly controlled the AAIW heat budget in the tropical W‐Atlantic after a detour via the Southern Ocean. We speculate that the ocean heat redistribution via AAIW effectively dampened Southern Hemisphere warming during the deglaciation and may therefore have been a crucial player in the climate seesaw mechanisms between the two hemispheres.

New records of stable silicon isotope signatures (δ30Si) together with concentrations of biogenic opal and organic carbon from the central (9° S) and northern (5° S) Peruvian margin reveal changes in diatom productivity and nutrient utilization during the past 20,000 years. The findings are based on a new approach using the difference between the δ30Si signatures of small (11-32μm) and large (>150μm) diatom fractions (Δ30Sicoscino-bSi) in combination with the variance in diatom assemblages for reconstruction of past upwelling intensity. Combination of our records with two previously published records from the southern upwelling area off Peru (12-15° S) shows a general decoupling of the environmental conditions at the central and southern shelf mainly caused by a northward shift of the main upwelling cell from its modern position (12-15° S) towards 9° S during Termination 1. At this time only moderate upwelling intensity and productivity levels prevailed between 9° S and 12° S interpreted by a more northerly position of Southern Westerly Winds and the South Pacific Subtropical High. Furthermore, a marked decrease in productivity at 12-15° S during Heinrich Stadial 1 coincided with enhanced biogenic opal production in the Eastern Equatorial Pacific, which was induced by a southward shift of the Intertropical Convergence zone and enhanced northeasterly trade winds. Modern conditions were only established at the onset of the Holocene. Past changes in preformed δ30Si signatures of subsurface waters reaching the Peruvian Upwelling System did not significantly affect the preserved δ30Si signatures.

The Kuroshio Current (KC) is the northward branch of the North Pacific subtropical gyre (NPG) and exerts influence on the exchange of physical, chemical, and biological properties of downstream regions in the Pacific Ocean. Resolving long-term changes in the flow of the KC water masses is, therefore, crucial for advancing our understanding of the Pacific's role in global ocean and climate variability. Here, we reconstruct changes in KC dynamics over the past 20 ka based on grain-size spectra, clay mineral, and Sr–Nd isotope constraints of sediments from the northern Okinawa Trough. Combined with published sediment records surrounding the NPG, we suggest that the KC remained in the Okinawa Trough throughout the Last Glacial Maximum. Together with Earth-System-Model simulations, our results additionally indicate that KC intensified considerably during the early Holocene (EH). The synchronous establishment of the KC “water barrier” and the modern circulation pattern during the EH highstand shaped the sediment transport patterns. This is ascribed to the precession-induced increase in the occurrence of La Nina-like state and the strength of the East Asian summer monsoon. The synchronicity of the shifts in the intensity of the KC, Kuroshio extension, and El Nino/La Nina-Southern Oscillation (ENSO) variability may further indicate that the western branch of the NPG has been subject to basin-scale changes in wind stress curl over the North Pacific in response to low-latitude insolation. Superimposed on this long-term trend are high-amplitude, large century, and millennial-scale variations during last 5 ka, which are ascribed to the advent of modern ENSO when the equatorial oceans experienced stronger insolation during the boreal winter.

Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

Water mass exchange between the Arctic Ocean and the Norwegian-Greenland Seas has played an important role for the Atlantic thermohaline circulation and Northern Hemisphere climate. We reconstruct past water mass mixing and erosional inputs from the radiogenic isotope compositions of neodymium (Nd), lead (Pb), and strontium (Sr) at Ocean Drilling Program site 911 (leg 151) from 906 m water depth on Yermak Plateau in the Fram Strait over the past 5.2 Myr. The isotopic compositions of past bottom waters were extracted from authigenic oxyhydroxide coatings of the bulk sediments. Neodymium isotope signatures obtained from surface sediments agree well with present-day deepwater eNd signature of −11.0 ± 0.2. Prior to 2.7 Ma the Nd and Pb isotope compositions of the bottom waters only show small variations indicative of a consistent influence of Atlantic waters. Since the major intensification of the Northern Hemisphere Glaciation at 2.7 Ma the seawater Nd isotope composition has varied more pronouncedly due to changes in weathering inputs related to the waxing and waning of the ice sheets on Svalbard, the Barents Sea, and the Eurasian shelf, due to changes in water mass exchange and due to the increasing supply of ice-rafted debris (IRD) originating from the Arctic Ocean. The seawater Pb isotope record also exhibits a higher short-term variability after 2.7 Ma, but there is also a trend toward more radiogenic values, which reflects a combination of changes in input sources and enhanced incongruent weathering inputs of Pb released from freshly eroded old continental rocks.

Highlights • Ba/Ca and δ18OSW records of Core SK 168 reveal distinct changes in SAM intensity. • SAM over the Irrawaddy strengthened beginning at ∼18 ka leading observed changes in the Arabian sea by ∼2–3 kyrs. • Peak monsoon strength during the mid-Holocene in the Andaman Sea consistent with model simulations. • Changes in upper ocean stratification indicate limited influence of NH insolation. Abstract The past variability of the South Asian Monsoon is mostly known from records of wind strength over the Arabian Sea while high-resolution paleorecords from regions of strong monsoon precipitation are still lacking. Here, we present records of past monsoon variability obtained from sediment core SK 168/GC-1, which was collected at the Alcock Seamount complex in the Andaman Sea. We utilize the ecological habitats of different planktic foraminiferal species to reconstruct freshwater-induced stratification based on paired Mg/Ca and δ18O analyses and to estimate seawater δ18O (δ18Osw). The difference between surface and thermocline temperatures (ΔT) and δ18Osw (Δδ18Osw) is used to investigate changes in upper ocean stratification. Additionally, Ba/Ca in G. sacculifer tests is used as a direct proxy for riverine runoff and sea surface salinity (SSS) changes related to monsoon precipitation on land. Our Δδ18Osw time series reveals that upper ocean salinity stratification did not change significantly throughout the last glacial suggesting little influence of NH insolation changes. The strongest increase in temperature gradients between the mixed layer and the thermocline is recorded for the mid-Holocene and indicate the presence of a significantly shallower thermocline. In line with previous work, the δ18Osw and Ba/Ca records demonstrate that monsoon climate during the LGM was characterized by a significantly weaker southwest monsoon circulation and strongly reduced runoff. Based on our data the South Asian Summer Monsoon (SAM) over the Irrawaddyy strengthened gradually after the LGM beginning at ∼18 ka. This is some 3 kyrs before an increase of the Ba/Ca record from the Arabian Sea and indicates that South Asian Monsoon climate dynamics are more complex than the simple N-S displacement of the ITCZ as generally described for other regions. Minimum δ18Osw values recorded during the mid-Holocene are in phase with Ba/Ca marking a stronger monsoon precipitation, which is consistent with model simulations.

Despite a clear correlation of alkenone unsaturation and sea surface temperatures (SST) throughout most parts of the ocean, scatter of the regression for various calibration equations has been shown to increase significantly at low SSTs. In this study, we combine previously published (n = 101) and new (n = 51) surface sediment data from the northern North Atlantic to constrain uncertainties of alkenone paleothermometry at low SSTs and to discuss possible sources of the increased scatter in the regression. The correlation between alkenone unsaturation and SSTs is strongest, in particular at the cold end (SSTs

International audience; In this study we combine for the first time silicon (Si) isotope compositions of small mixed diatom species (d 30 Si bSiO2) and of large handpicked mono-generic (i.e. genus = Coscinodiscus) diatom samples (d 30 Si Coscino) with diatom assemblages extracted from marine sediments in the Peruvian upwelling region in order to constrain present and past silicate utilisation. The extension of a previous core-top data set from the Peruvian shelf demonstrates that d 30 Si Coscino values record near-complete Si utilisation, as these are similar to the isotopic composition of the subsurface source waters feeding the upwelling. In contrast, the d 30 Si bSiO2 of small mixed diatom species increase southward along the shelf as well as towards the shore. We attribute highest d 30 Si bSiO2 values partly to transient iron limitation but primarily to the gradual increase of Si isotope frac-tionation within the seasonal diatom succession, which are mainly recorded by small diatom species during intense bloom events. In contrast, lower d 30 Si bSiO2 values are related to initial Si isotope utilisation during periods of weak upwelling, when low Si(OH) 4 concentrations do not permit intense blooms and small diatom species record substantially lower d 30 Si signatures. As such, we propose that the intensity of the upwelling can be deduced from the offset between d 30 Si bSiO2 and d 30 Si Coscino (D 30 Si coscino-bSiO2), which is low for strong upwelling conditions and high for prevailing weak upwelling. We apply the information extracted from surface sediments to generate a record of the present-day main upwelling region covering the past 17,700 years and find that this location has also been characterized by a persistent offset (D 30 Si coscino-bSiO2). By comparison with the diatom assemblages we show that the coastal upwelling system changed markedly between weak and strong upwelling conditions. In addition, our model calculations to quantify species-specific Si isotope fractionation effects based on the diatom assemblages indicate an overall minor influence that cannot explain the high amplitude in the measured d 30 Si bSiO2 record.

Highlights • We present a Ba isotope data set of seawater, river waters and biogenic particles. • Ba isotope signatures of upper ocean waters are heavier than river and deep waters. • Adsorption of lighter Ba isotopes on biogenic particles induces the fractionation. • Ba isotopes trace land–sea interactions and ocean mixing processes. • Decoupling of Ba from major nutrients confirms Ba to be a biointermediate element. Abstract The distribution of barium (Ba) concentrations in seawater resembles that of nutrients and Ba has been widely used as a proxy of paleoproductivity. However, the exact mechanisms controlling the nutrient-like behavior, and thus the fundamentals of Ba chemistry in the ocean, have not been fully resolved. Here we present a set of full water column dissolved Ba (DBa) isotope (δ137BaDBa) profiles from the South China Sea and the East China Sea that receives large freshwater inputs from the Changjiang (Yangtze River). We find pronounced and systematic horizontal and depth dependent δ137BaDBa gradients. Beyond the river influence characterized by generally light signatures (0.0 to +0.3‰+0.3‰), the δ137BaDBa values in the upper water column are significantly higher (+0.9‰+0.9‰) than those in the deep waters (+0.5‰+0.5‰). Moreover, δ137BaDBa signatures are essentially constant in the entire upper 100 m, in which dissolved silicon isotopes are fractionated during diatom growth resulting in the heaviest isotopic compositions in the very surface waters. Combined with the decoupling of DBa concentrations and δ137BaDBa from the concentrations of nitrate and phosphate this implies that the apparent nutrient-like fractionation of Ba isotopes in seawater is primarily induced by preferential adsorption of the lighter isotopes onto biogenic particles rather than by biological utilization. The subsurface δ137BaDBa distribution is dominated by water mass mixing. The application of stable Ba isotopes as a proxy for nutrient cycling should therefore be considered with caution and both biological and physical processes need to be considered. Clearly, however, Ba isotopes show great potential as a new tracer for land–sea interactions and ocean mixing processes.

Marine sediments deposited off the Zambezi River that drains a considerable part of the southeast African continent provide continuous records of the continental climatic and environmental conditions. Here we present time series of neodymium (Nd) isotope signatures of the detrital sediment fraction during the past ~45,000 years, to reconstruct climate-driven changes in the provenance of clays deposited along the Mozambique Margin. Coherent with the surface current regime, the Nd isotope distribution in surface sediments reveals mixing of the alongshore flowing Zambezi suspension load with sediments supplied by smaller rivers located further north. To reconstruct past changes in sediment provenances, Nd isotope signatures of clays that are not significantly fractionated during weathering processes have been obtained from core 64PE304-80, which was recovered just north of the Zambezi mouth at 1329 m water depth. Distinctly unradiogenic clay signatures (ENd values

Stable carbon and oxygen isotopes (δ13C and δ18O) of foraminiferal tests are amongst the most important tools in paleoceanography, but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here we compare three middle Miocene (16–13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicates continued diagenetic alteration in sediments > 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high-resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (< 100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and δ18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well-resolved paleomagnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global geological timescale.