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  • 2020-2024  (130)
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  • 1
    Publication Date: 2023-07-19
    Description: Limited constraints on the variability of the deep‐water production in the Labrador Sea complicate reconstructions of the strength of the Atlantic Meridional Overturning Circulation (AMOC) during the Late Quaternary. Large volumes of detrital carbonates were repeatedly deposited in the Labrador Sea during the last 32 kyr, potentially affecting radiogenic Nd isotope signatures. To investigate this the Nd isotope compositions of deep and intermediate waters were extracted from the authigenic Fe‐Mn oxyhydroxide fraction, foraminiferal coatings, the residual silicates and leachates of dolostone grains. We provide a first order estimation of Nd release via dissolution of detrital carbonates and its contribution to the authigenic ԑNd signatures in the Labrador Sea. During the Last Glacial Maximum the Nd isotope signatures in the Labrador Sea would allow active water mass mixing with more radiogenic ɛNd values (−12.6 and −14) prevailing in its eastern part whereas less radiogenic values (ɛNd ∼ −18.4) were found on the western Labrador slope. The deposition of detrital carbonates during Heinrich stadials (2,1) was accompanied by negative detrital and authigenic Nd isotope excursions (ɛNd ∼ −31) that were likely controlled by dissolution of dolostone or dolostone associated mineral inclusions. This highly unradiogenic signal dominated the authigenic phases and individual water masses in the Labrador Sea, serving as potential source of highly unradiogenic Nd to the North Atlantic region, while exported southward. The Holocene authigenic ɛNd signatures of the coatings and leachates significantly differed from those of the detrital silicates, approaching modern bottom water mass signatures during the Late Holocene.
    Description: Plain Language Summary: The Labrador Sea is an important region for deep water formation and for the ocean circulation in the Atlantic region. Over the last 32 thousand years, numerous discharges from melting glaciers added freshwater to the Labrador Sea which could help understand the future effects of current melting glaciers. This information is necessary to better constrain climate predictions in order to gauge the effects on the Global Ocean Water Circulation. However, past deep water production in the Labrador is still poorly constrained, complicating reconstruction of the Atlantic Meridional Overturning Circulation on different timescales. In this study we investigated changes in deep and intermediate water mass circulation patterns over the last 32 kyr based on the radiogenic Nd isotope compositions that serve as a water mass circulation proxy. Analysis of four marine sediment cores show that the deposition of large volumes of detrital carbonates during studied period had a large effect on the recorded in the sediment column signals. New data suggest active water mass circulation during the maximum extent of glacial ice sheets. The modern day ocean circulation patterns have emerged during the Late Holocene (6 ka).
    Description: Key Points: Estimation of Nd release via dissolution of detrital carbonates and its contribution to the authigenic ԑNd signatures in the Labrador Sea. Dissolution of detrital dolostones in the water column during Heinrich stadials at least partially controlled ɛNd signatures. During the LGM generally more radiogenic signatures possibly indicate active water mass advection and mixing in the Labrador Sea.
    Description: GEOMAR Helmholtz‐Zentrum für Ozeanforschung Kiel http://dx.doi.org/10.13039/501100003153
    Description: Kiel University
    Description: https://doi.org/10.1594/PANGAEA.952659
    Keywords: ddc:551.9 ; Labrador Sea ; Late Quaternary ; Paleoceanography ; neodymium isotopes ; dolostone ; AMOC ; carbonate dissolution ; Heinrich stadials
    Language: English
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  • 2
    Publication Date: 2023-02-08
    Description: Estuarine systems are of key importance for the riverine input of silicon (Si) to the ocean, which is a limiting factor of diatom productivity in coastal areas. This study presents a field dataset of surface dissolved Si isotopic compositions (30SiSi(OH)4) obtained in the estuaries of three of the world’s largest rivers, the Amazon (ARE), Yangtze (YRE), and Pearl (PRE), which cover different climate zones. While 30SiSi(OH)4 behaved conservatively in the YRE and PRE supporting a dominant control by water mass mixing, significantly increased 30SiSi(OH)4 signatures due to diatom utilization of Si(OH)4 were observed in the ARE and reflected a Si isotopic enrichment factor 30 of −1.0±0.4‰ (Rayleigh model) or −1.6±0.4‰ (steady state model). In addition, seasonal variability of Si isotope behavior in the YRE was observed by comparison to previous work and most likely resulted from changes in water residence time, temperature, and light level. Based on the 30 value obtained for the ARE, we estimate that the global average 30SiSi(OH)4 entering the ocean is 0.2-0.3‰ higher than that of the rivers due to Si retention in estuaries. This systematic modification of riverine Si isotopic compositions during estuarine mixing, as well as the seasonality of Si isotope dynamics in single estuaries, needs to be taken into account for better constraining the role of large river estuaries in the oceanic Si cycle.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2023-02-08
    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.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2023-02-08
    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.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2023-02-08
    Type: Article , PeerReviewed
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  • 6
    Publication Date: 2023-02-08
    Description: Key Points Calibration of XRF core scanning data highlights the need for careful examination of sediment properties such as porosity/water Grain size and water content in the sediment trigger systematic artifacts in the signal intensity of light elements (e.g. Si and Al) Known terrigenous flux proxies (e.g Ti/Ca, Fe/Ca) are influenced by sea level variations X‐ray fluorescence (XRF) core scanning of marine and lake sediments has been extensively used to study changes in past environmental and climatic processes over a range of timescales. The interpretation of XRF‐derived element ratios in paleoclimatic and paleoceanographic studies primarily considers differences in the relative abundances of particular elements. Here we present new XRF core scanning data from two long sediment cores in the Andaman Sea in the northern Indian Ocean and show that sea level related processes influence terrigenous inputs based proxies such as Ti/Ca, Fe/Ca, and elemental concentrations of the transition metals (e.g. Mn). Zr/Rb ratios are mainly a function of changes in median grain size of lithogenic particles and often covary with changes in Ca concentrations that reflect changes in biogenic calcium carbonate production. This suggests that a common process (i.e. sea level) influences both records. The interpretation of lighter element data (e.g. Si and Al) based on low XRF counts is complicated as variations in mean grain size and water content result in systematic artifacts and signal intensities not related to the Al or Si content of the sediments. This highlights the need for calibration of XRF core scanning data based on discrete sample analyses and careful examination of sediment properties such as porosity/water content for reliably disentangling environmental signals from other physical properties. In the case of the Andaman Sea, reliable extraction of a monsoon signal will require accounting for the sea level influence on the XRF data.
    Type: Article , PeerReviewed
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  • 7
    Publication Date: 2023-02-08
    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.
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  • 8
    Publication Date: 2023-02-08
    Description: Highlights • First systematic dissolved neodymium isotope distributions in Angola and Cape Basins. • Deep water neodymium isotopes dominated by conservative mixing in study area. • Neodymium isotopes trace surface waters from Mozambique Channel in Angola Basin. • Cape Basin bottom water neodymium isotopes are unaffected by neodymium from sediments. • Glacial Cape Basin bottom waters may show effects of sedimentary neodymium inputs. Abstract In contrast to the vigorous deep ocean circulation system of the north- and southwestern Atlantic Ocean, no systematically sampled datasets of dissolved radiogenic neodymium (Nd) isotope signatures exist to trace water mass mixing and provenance for the more restricted and less well ventilated Angola Basin and the Cape Basin in the southeastern Atlantic Ocean, where important parts of the return flow of the Atlantic Meridional Overturning Circulation are generated. Here, to improve our understanding of water mass mixing and provenance, we present the first full water column Nd isotope (expressed as εNd values) and concentration data for a section across the western Angola Basin from 3° to 30° S along the Zero Meridian and along an E-W section across the northern Cape Basin at 30° S sampled during GEOTRACES cruise GA08. Compared with the southwestern Atlantic basin we find overall less radiogenic εNd signatures reaching −17.6 in the uppermost 200 m of the Angola and Cape basins. In the western Angola Basin these signatures are the consequence of the admixture of a coastal plume originating near 13° S and carrying an unradiogenic Nd signal that likely resulted from the dissolution of Fe-Mn coatings of particles formed in river estuaries or near the West African coast. The highly unradiogenic Nd isotope signatures in the upper water column of the northern Cape Basin, in contrast, originate from old Archean terrains of southern Africa and are introduced into the Mozambique Channel via rivers like the Limpopo and Zambezi. These signatures allow tracing the advection of shallow waters via the Agulhas and Benguela currents into the southeastern Atlantic Ocean. The Nd isotope compositions of the deep water masses in both basins primarily reflect conservative water mass mixing with the only exception being the central Angola Basin, where the signatures are significantly overprinted by terrestrial inputs. Bottom waters of the Cape Basin show excess Nd concentrations of up to 6 pmol/kg (20%), originating from resuspended bottom sediments and/or dissolution of dust, but without significantly changing the isotopic composition of the waters due to similar εNd values of particles and bottom waters ranging between −9.6 and −10.5. Given that bottom waters within the Cape Basin today are enriched in Nd, non-conservative Nd isotopic effects may have been resolvable under past glacial boundary conditions when bottom waters were more radiogenic.
    Type: Article , PeerReviewed
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  • 9
    Publication Date: 2023-02-08
    Description: 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. Remineralized 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 records that allow fingerprinting of water masses and provide a more complete picture of the Atlantic Meridional Overturning Circulation geometry during the Last Glacial Maximum. These results suggest that the vertical and meridional structure of the Atlantic 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 had been previously inferred from stable carbon isotope (δ13C) 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, corroborating previous evidence.
    Type: Article , PeerReviewed
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  • 10
    Publication Date: 2023-02-08
    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.
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