Description: The stable silicon isotopic composition (δ30Si) of waters and diatoms has increasingly been used to investigate the biogeochemical cycling of Si in the major ocean basins. Here we present the first Si isotope data set from the northern South China Sea (NSCS), a large marginal sea system in the western North Pacific to examine sources and utilization of silicic acid (Si(OH)4). During two cruises in July–August 2009 (summer) and January 2010 (winter), samples for isotope measurements of dissolved Si(OH)4 (δ30SiSi(OH)4) and of biogenic silica (δ30SiBSi) in suspended particles were collected along a transect perpendicular to the coast from the inner shelf to the deep-water slope, as well as at the South East Asian Time-series Study (SEATS) station located in the NSCS basin. Surface δ30SiSi(OH)4 generally increased from values ∼+2.3‰ on the inner shelf to ∼+2.8‰ above the deep basin, suggesting an increasing utilization of dissolved Si(OH)4 reflecting the transition from eutrophic to oligotrophic conditions. The δ30SiBSi values were systematically lower than the corresponding δ30SiSi(OH)4 in the euphotic zone (above 100 m) on the shelf and slope. In contrast at station SEATS in the NSCS basin, δ30SiBSi signatures in both seasons were within error equal to δ30SiSi(OH)4 in the surface mixed layer (above 50 m) and δ30SiBSi in waters below were significantly higher than the corresponding δ30SiSi(OH)4. By comparing the field data with the Si isotope fractionation revealed by the Rayleigh or the steady state models, we demonstrate the existence of variable Si(OH)4 origins in different areas of the NSCS. Surface waters on the inner shelf were largely fed by nutrients from the Pearl River input. While the primary source of Si(OH)4 for the euphotic zone on the outer shelf and slope was upwelling or vertical mixing from underlying waters, the Si(OH)4 in the surface mixed layer of the NSCS basin might have originated from horizontal mixing with other highly fractionated surface waters. As a consequence, the Si isotope dynamics in the NSCS are largely controlled by variable biological fractionation of Si in waters from different sources with different initial Si isotopic compositions rather than any single source water.

Description: Sediments deposited on deep-sea fans are an excellent geological archive to reconstruct past changes in fluvial discharge. Here we present a reconstruction of changes in the regime of the Nile River during the Holocene obtained using bulk elemental composition, grain-size analyses and radiogenic strontium (Sr) and neodymium (Nd) isotopes from a sediment core collected on the Nile deep-sea fan. This 6-m long core was retrieved at View the MathML source water-depth and is characterized by the presence of a 5-m thick section of finely laminated sediments, which were deposited between 9.5 and 7.3 ka BP and correspond to the African Humid Period (AHP). The data show distinct changes in eolian dust inputs as well as variations in discharge of the Blue Nile and White Nile. Sedimentation was mainly controlled by changes in fluvial discharge during the Holocene, which was predominantly forced by low-latitude summer insolation and by the location of the eastern African Rain Belt. The changes in relative contribution from the Blue Nile and White Nile followed changes in low-latitude spring/autumn insolation, which highlights the role of changes in seasonality of the precipitation on the Nile River regime. The relative intensity of the Blue Nile discharge was enhanced during the early and late Holocene at times of higher spring insolation (with massive erosion and runoff during the AHP at times of high summer insolation), while it was reduced between 8 and 4 ka at times of high autumn insolation. The gradual insolation-paced changes in fluvial regime were interrupted by a short-term arid event at 8.5–7.3 ka BP (also associated with rejuvenation of bottom-water ventilation above the Nile fan), which was likely related to northern hemisphere cooling events. Another arid event at 4.5–3.7 ka BP occurred as the apex of a gradually drier phase in NE Africa and marks the end of the AHP.

Description: We integrate micropaleontological and geochemical records (benthic stable isotopes, neodymium isotopes, benthic foraminiferal abundances and XRF-scanner derived elemental data) from well-dated Pacific Ocean successions (15–12.7 Ma) to monitor circulation changes during the middle Miocene transition into a colder climate mode with permanent Antarctic ice cover. Together with previously published records, our results show improvement in deep water ventilation and strengthening of the meridional overturning circulation following major ice expansion at ∼13.9 Ma. Neodymium isotope data reveal, however, that the provenance of intermediate and deep water masses did not change markedly between 15 and 12.7 Ma. We attribute the increased δ13C gradient between Pacific deep and intermediate water masses between ∼13.6 and 12.7 Ma to more vigorous entrainment of Pacific Central Water into the wind-driven ocean circulation due to enhanced production of intermediate and deep waters in the Southern Ocean. Prominent 100 kyr ventilation cycles after 13.9 Ma reveal that the deep Pacific remained poorly ventilated during warmer intervals at high eccentricity, whereas colder periods (low eccentricity) were characterized by a more vigorous meridional overturning circulation with enhanced carbonate preservation. The long-term δ13C decline in Pacific intermediate and deep water sites between 13.5 and 12.7 Ma reflects a global trend, probably related to a re-adjustment response of the global carbon cycle following the last 400 kyr carbon maximum (CM6) of the “Monterey Excursion”.

Description: The radiogenic neodymium (Nd) isotope composition of foraminiferal shells provides a powerful archive to investigate past changes in sources and mixing of water masses. However, seawater Nd isotope ratios extracted from foraminiferal shells can be biased by contaminant phases such as organic matter, silicates, or ferromanganese coatings, the removal of which requires rigorous multiple step cleaning of the samples. Here we investigate the efficiency of Flow Through and batch cleaning methods to extract seawater Nd isotope compositions from planktonic foraminifera in a shelf setting in the Gulf of Guinea that is strongly influenced by riverine sediment inputs. Nd isotope analyses of reductively and oxidatively cleaned mono-specific planktonic foraminiferal samples and reductively cleaned mixed benthic foraminifera were complemented by analyses of non-reductively cleaned mono-specific planktonic foraminiferal samples, Fe–Mn coatings of de-carbonated bulk sediment leachates, and the residual detrital fraction of the same sediment. Al/Ca and Mn/Ca ratios of fully cleaned foraminiferal samples reveal indistinguishable levels of cleaning efficiency between the batch and the Flow Through methods and the Nd isotope compositions obtained from application of both methods are identical within error. Furthermore, non-reductively cleaned foraminiferal samples have the same Nd isotope composition as reductively cleaned foraminifera at our study sites. Close to the Niger River mouth the Nd isotope composition of the foraminifera agree with the seawater Nd isotope composition of nearby stations. Based on the combined extracted Nd isotope signatures and element to calcium ratios, as well as rare earth element distribution patterns, we infer that the planktonic foraminiferal Nd isotope signatures reflect bottom water/pore water signatures. The isotopic composition of the bulk de-carbonated sediment leachates (Fe–Mn coatings) differs significantly from the foraminiferal data at this site and probably reflects particles that acquired their ferromanganese/pre-formed pre-formed/ferromanganese coatings in nearby rivers. Therefore, in such river influenced shelf settings foraminiferal shells should be used to obtain unbiased bottom seawater signatures.

Description: The recrystallisation (dissolution–precipitation) of carbonate sediments has been successfully modelled to explain profiles of pore water Sr concentration and radiogenic Sr isotope composition at different locations of the global ocean. However, there have been few systematic studies trying to better understand the relative importance of factors influencing the variability of carbonate recrystallisation. Here we present results from a multi-component study of recrystallisation in sediments from the Integrated Ocean Drilling Program (IODP) Expedition 320/321 Pacific Equatorial Age Transect (PEAT), where sediments of similar initial composition have been subjected to different diagenetic histories. The PEAT sites investigated exhibit variable pore water Sr concentrations gradients with the largest gradients in the youngest sites. Radiogenic Sr isotopes suggest recrystallisation was relative rapid, consistent with modelling of other sediment columns, as the 87Sr/86Sr ratios are indistinguishable (within 2σ uncertainties) from contemporaneous seawater 87Sr/86Sr ratios. Bulk carbonate leachates and associated pore waters of Site U1336 have lower 87Sr/86Sr ratios than contemporaneous seawater in sediments older than 20.2 Ma most likely resulting from the upward diffusion of Sr from older recrystallised carbonates. It seems that recrystallisation at Site U1336 may still be on-going at depths below 102.5 rmcd (revised metres composite depth) suggesting a late phase of recrystallisation. Furthermore, the lower Sr/Ca ratios of bulk carbonates of Site U1336 compared to the other PEAT sites suggest more extensive diagenetic alteration as less Sr is incorporated into secondary calcite. Compared to the other PEAT sites, U1336 has an inferred greater thermal gradient and a higher carbonate content. The enhanced thermal gradient seems to have made these sediments more reactive and enhanced recrystallisation. In this study we investigate stable Sr isotopes from carbonate-rich deep sea sediments for the first time. Pore water δ88/86Sr increases with depth (from 0.428‰ to values reaching up to 0.700‰) at Site U1336 documenting an isotope fractionation process during recrystallisation. Secondary calcite preferentially incorporates the lighter Sr isotope (86Sr) leaving pore waters isotopically heavy. The δ88/86Sr values of the carbonates themselves show more uniform values with no detectable change with depth. Carbonates have a much higher Sr content and total Sr inventory than the pore waters meaning pore waters are much more sensitive to fractionation processes than the carbonates. The δ88/86Sr results indicate that pore water stable Sr isotopes have the potential to indicate the recrystallisation of carbonate sediments.

Description: Highlights • Seawater Hf–Nd–Pb isotopic evolution in the deep Arctic Ocean of the past 7 Myr. • Climatically driven changes in weathering inputs since 4 Ma. • North American (Laurentide Ice Sheet) runoff controlled the isotopic budget in the Canada Basin. • More congruent Hf release due to glacial weathering conditions. • Past Arctic Ocean water masses show larger isotopic differences than today. Abstract We present the first continuous records of dissolved radiogenic neodymium, hafnium, and lead isotope compositions of deep waters in the western Arctic Ocean, spanning the time from the late Miocene to the present. The data were obtained from three hydrogenetic ferromanganese (Fe–Mn) crusts recovered from seamounts along the northernmost edge of the Northwind Ridge in the Canada Basin from water depths of 2200, 2400, and 3600 m. Dating the crusts using cosmogenic 10Be documents undisturbed present-day growth surfaces and yields growth rates between 27 and 2.2 mm/Myr. The Nd (Hf) isotope time series of the three crusts show similar evolutions from εNdεNd(εHf)(εHf) of −8.5 (+4) in the oldest parts to −11.5 (−4) at the surfaces and a pronounced trend to less radiogenic values starting at ∼4 Ma. This coincided with a trend of the Pb isotope evolution towards more radiogenic 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb. It is inferred that climatically controlled changes in weathering regime and sediment transport along the North American continent were responsible for the major change of the radiogenic isotope composition of the Arctic Deep Water (ADW) in the Canada Basin. Based on these records we conclude that weathering inputs from the North American continent linked to enhanced glacial conditions started to increase and to influence the radiogenic isotope composition of ADW ∼4 million years ago and were further intensified at ∼1 Ma. These new time series differ markedly from the radiogenic isotope evolution of Arctic Intermediate Water recorded on the Lomonosov Ridge and suggest that much larger isotopic differences between the water masses of the Arctic Ocean than today prevailed in the past.

Description: Since the inception of the international GEOTRACES program, studies investigating the distribution of trace elements and their isotopes in the global ocean have significantly increased. In spite of this large-scale effort, the distribution of neodymium isotopes (143Nd/144Nd, εNd) and concentrations ([Nd]) in the high latitude South Pacific is still understudied, specifically north of the Antarctic Polar Front (APF). Here we report dissolved Nd isotopes and concentrations from 11 vertical water column profiles from the South Pacific between South America and New Zealand and across the Antarctic frontal system. Results confirm that Ross Sea Bottom Water (RSBW) is represented by an εNdvalue of ∼−7, and for the first time show that these Nd characteristics can be traced into the Southeast Pacific until progressive mixing with ambient Lower Circumpolar Deep Water (LCDW) dilutes this signal north of the APF. That is, εNdbehaves conservatively in RSBW, opening a path for studies of past RSBW behavior. Neodymium concentrations show low surface concentrations and a linear increase with depth north of the APF. South of the APF, surface [Nd] is high and increases with depth but remains almost constant below ∼1000m. This vertical and spatial [Nd] pattern follows the southward shoaling density surfaces of the Southern Ocean and hence suggests supply of Nd to the upper ocean through upwelling of Nd-rich deep water. Low particle abundance due to reduced opal production and seasonal sea ice cover likely contributes to the maintenance of the high upper ocean [Nd] south of the APF. This suggests a dominant lateral transport component on [Nd] and a reduced vertical control on Nd concentrations in the South Pacific south of the APF.

Description: Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANTXXIV/3 and ANTXXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (〈0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labeled by terrigenous inputs. Near South Africa Nd isotope values as low as εNd = −18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to εHf = 6.1 and εNd = −4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (εNd ∼ −8 to −8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Passage. The Hf isotope compositions in the entire study area only show a small range between εHf = + 6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from εNd = −18.9 to −4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.

Description: It is well established that Hf weathers incongruently such that the isotopic compositions in seawater are offset from those of Nd relative to the correlation defined by bulk lithologies of the continental crust. Here we study this process in detail with new records of the seasonal variability of isotope compositions and concentrations of Hf and Nd in four Swiss rivers. The water has been filtered at a pore size of 0.45 mu m and therefore represents the truly dissolved and the colloidal pool of both elements. The studied rivers drain metamorphic (gneissic) or sedimentary (mixed carbonate/siliciclastic) lithologies. The dissolved isotope data are compared to the isotope compositions and concentrations of the suspended load and different fractions of the actual source rocks in the respective catchments, as well as to concomitant changes in the aqueous chemistry of the major elements. Dissolved Nd concentrations span similar ranges for all rivers, whereas Hf concentrations are one order of magnitude lower in the rivers that drain gneissic catchments compared to those draining sedimentary rocks. This primarily results from the retention of most of the Hf in the gneissic zircons, as indicated by the Hf budget of the gneisses, whereas Hf in the sedimentary catchments is readily weathered from fine detrital silicates. Large differences are found between the dissolved Hf isotope compositions of the rivers and those of the suspended load and the source rocks, consistent with the release of Hf from a radiogenic rock fraction during weathering. In the metamorphic catchments this primarily reflects that fact that zircons are barely accessible for weathering. The zircon-free portion of the rocks appears to weather congruently as the riverine Hf isotope compositions are similar to the zircon-free portion of the gneisses, rather than being distinctly more radiogenic. Leaching experiments performed to understand the riverine Hf budget in the sedimentary catchments reveal that the carbonate fraction of the sedimentary rocks is extremely radiogenic, yielding Hf isotope compositions up to epsilon(Hf) of + 208. However, the Hf concentrations in the carbonate fractions are too low to dominate the riverine Hf budget, which is instead controlled by the weathering of detrital silicate minerals. Two of the catchments, a metamorphic and a sedimentary one, show relatively systematic changes towards more radiogenic dissolved Hf isotope compositions as discharge increases. This suggests that continental runoff conditions could be a relevant parameter for the control of the seawater Hf isotope composition, whereby more congruent weathering is achieved during low discharge when Hf is increasingly derived from weathering-resistant unradiogenic minerals

Description: Using the TANDY AMS facility (600 kV) at ETH Zurich the seawater-derived (authigenic) Be-10/Be-9 ratio of marine sediment samples is measured without the addition of Be-9 carrier. This novel method reduces systematic uncertainties because the Be-10/Be-9 ratio of a sample is determined in only one (AMS) measurement. A challenge of carrier-free AMS is to avoid any contamination of the sample with Be-9 during the chemical preparation. Further, the leaching procedure has to be reproducible and ideally should attack the authigenic Be of the sediments only, leaving the detrital Be untouched. The low amount of stable Be-9 in the unspiked samples causes low currents during the AMS measurement. This requires a good stability and sensitivity of the AMS setup. Our first results show that the new preparation method is reliable and that background from stable Be-9 is avoided. For a comparison study, sediment samples from two cores located in the Arctic Ocean (HLY0503-09JPC, HLY0503-14JPC) were used. The authigenic Be-10/Be-9 ratio of these samples had been determined previously applying the conventional method where Be-10 and Be-9 concentrations are measured separately by AMS and ICP-MS, respectively. The resulting sedimentation rates are in discrepancy with values derived from biomarkers. To cross check the Be-10/Be-9 based age model two samples from each core were measured again with the new carrier-free method. The carrier-free results show systematically higher authigenic Be-10/Be-9 ratios. The calculated sedimentation rates of about 0.2 cm/kyr, however, are consistent for the carrier free and the conventional method.