Description: 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 (BoB) and the Andaman Sea (AnS), we have analyzed the yttrium and rare earth element (YREE) concentration of surface seawater samples from various locations spanning the Andaman Islands in 2011 to 2013. In some locations, samples have been taken in March, July, and November 2011, thus spanning the seasonal cycle and including different monsoon phases. Generally, the YREE patterns are similar to those reported for offshore samples from the BoB and AnS in January 1997, with seawater-normalized patterns of most samples characterized by middle REE enrichments. An enhancement of these middle REE bulges accompanies large increases in dissolved REE concentrations from streams and sediment-rich areas such as mangrove environments. Conversely, some samples, in particular those taken 1–2 days after heavy rainfall in March 2011, show pronounced REE scavenging accompanied by the preferential removal of dissolved light REEs (LREEs) and by higher Y/Ho ratios. The Nd isotope signature of the remaining dissolved REE phase of these low YREE samples is more radiogenic than local rocks and sediments. The time series at a location away from local input sources show remarkably similar REE patterns and concentrations in March and July. Then in October–November, following the peak in monsoon-induced river discharge, the dissolved REE concentrations increase by almost a factor of two, whereas Nd isotopes become less radiogenic by 1.5 εNd units. These unradiogenic values are found at the same site in the winter dry season of the following year, demonstrating the decoupling of sea surface salinity (SSS) and Nd. The large sub-annual variability of YREE concentrations and Nd isotopes encountered was likely caused by the conversion of YREE from the dissolved (probably colloidal) pool to the labile particulate fraction. The comparison of unfiltered and filtered sample concentrations reveals the existence of a large labile particulate pool in the BoB and AnS that most likely originates from the massive river sediment fluxes and is instrumental in the seasonal changes observed.

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

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

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

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

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

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

Description: Benthic fluxes of dissolved silica (Si) from sediments into the water column are driven by the dissolution of biogenic silica (bSiO2) and terrigenous Si minerals and modulated by the precipitation of authigenic Si phases. Each of these processes has a specific effect on the isotopic composition of silica dissolved in sediment pore waters such that the determination of pore water δ30Si values can help to decipher the complex Si cycle in surface sediments. In this study, the δ30Si signatures of pore fluids and bSiO2 in the Guaymas Basin (Gulf of California) were analyzed, which is characterized by high bSiO2 accumulation and hydrothermal activity. The δ30Si signatures were investigated in the deep basin, in the vicinity of a hydrothermal vent field, and at an anoxic site located within the pronounced oxygen minimum zone (OMZ). The pore fluid δ30Sipf signatures differ significantly depending on the ambient conditions. Within the basin, δ30Sipf is essentially uniform averaging +1.2 ± 0.1 ‰ (1SD). Pore fluid δ30Sipf values from within the OMZ are significantly lower (0.0 ± 0.5 ‰, 1SD), while pore fluids close to the hydrothermal vent field are higher (+2.0 ± 0.2 ‰, 1SD). Reactive transport modelling results show that the δ30Sipf is mainly controlled by silica dissolution (bSiO2 and terrigenous phases) and Si precipitation (authigenic aluminosilicates). Precipitation processes cause a shift to high pore fluid δ30Sipf signatures, most pronounced at the hydrothermal site. Within the OMZ however, additional dissolution of isotopically depleted Si minerals (e.g. clays) facilitated by high mass accumulation rates of terrigenous material (MARterr) is required to promote the low δ30Sipf signatures while precipitation of authigenic aluminosilicates seems to be hampered by high water / rock ratios. Guaymas OMZ δ30Sipf values are markedly different from those of the Peruvian OMZ, the only other marine setting where Si isotopes have been investigated to constrain early diagenetic processes. These differences highlight the fact that δ30Sipf signals in OMZs worldwide are not alike and each setting can result in a range of δ30Sipf values as a function of the environmental conditions. We conclude that the benthic silica cycle is more complex than previously thought and that additional Si isotope studies are needed to decipher the controls on Si turnover in marine sediment and the role of sediments in the marine silica cycle.

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