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  • 2020-2024  (72)
  • 2022  (42)
  • 2021  (30)
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  • 1
    Online Resource
    Online Resource
    Kiel : Universitätsbibliothek Kiel
    Keywords: Hochschulschrift
    Type of Medium: Online Resource
    Pages: 1 Online-Ressource (VIII, 226 Seiten) , Illustrationen
    DDC: 550
    Language: English
    Note: Kumulatives Verfahren, enthält 3 Aufsätze aus Zeitschriften
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  • 2
    Online Resource
    Online Resource
    Kiel : Universitätsbibliothek Kiel
    Keywords: Hochschulschrift ; Bariumisotop ; Biogeochemie ; Paläoozeanographie
    Type of Medium: Online Resource
    Pages: 1 Online-Ressource (v,147 Seiten) , Illustrationen
    DDC: 551.462
    Language: English
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  • 3
    Publication Date: 2024-02-07
    Description: 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.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2024-02-07
    Description: The upwelling area off Peru is characterized by exceptionally high rates of primary productivity, mainly dominated by diatoms, which require dissolved silicic acid (dSi) to construct their frustules. The silicon isotope compositions of dissolved silicic acid (δ 30 Si dSi ) and biogenic silica (δ 30 Si bSi ) in the ocean carry information about dSi utilization, dissolution, and water mass mixing. Diatoms are preserved in the underlying sediments and can serve as archives for past nutrient conditions. However, the factors influencing the Si isotope fractionation between diatoms and seawater are not fully understood. More δ 30 Si bSi data in today’s ocean are required to validate and improve the understanding of paleo records. Here, we present the first δ 30 Si bSi data (together with δ 30 Si dSi ) from the water column in the Peruvian Upwelling region. Samples were taken under strong upwelling conditions and the bSi collected from seawater consisted of more than 98% diatoms. The δ 30 Si dSi signatures in the surface waters were higher (+1.7‰ to +3.0‰) than δ 30 Si bSi (+1.0‰ to +2‰) with offsets between diatoms and seawater (Δ 30 Si) ranging from −0.4‰ to −1.0‰. In contrast, δ 30 Si dSi and δ 30 Si bSi signatures were similar in the subsurface waters of the oxygen minimum zone (OMZ) as a consequence of a decrease in δ 30 Si dSi . A strong relationship between δ 30 Si bSi and [dSi] in surface water samples supports that dSi utilization of the available pool (70 and 98%) is the main driver controlling δ 30 Si bSi . A comparison of δ 30 Si bSi samples from the water column and from underlying core-top sediments (δ 30 Si bSi_ sed. ) in the central upwelling region off Peru (10°S and 15°S) showed good agreement (δ 30 Si bSi_ sed. = +0.9‰ to +1.7‰), although we observed small differences in δ 30 Si bSi depending on the diatom size fraction and diatom assemblage. A detailed analysis of the diatom assemblages highlights apparent variability in fractionation among taxa that has to be taken into account when using δ 30 Si bSi data as a paleo proxy for the reconstruction of dSi utilization in the region.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2024-02-07
    Description: Highlights • Revised Nd implementation in the Bern3D model improves agreement with observations. • Dynamically consistent physical-biogeochemical framework including full Nd cycle. • Glacial Nd isotopes globally more radiogenic due to changed weathering input fluxes. • εNd behaved less conservatively during the glacial independent of the circulation. • Deglacial variability of the circulation best captured by εNd in the South Atlantic. Proxy reconstructions from deep ocean sediments have helped to shape our understanding of the role of the global overturning circulation in past climate change. Neodymium (Nd) isotopes have contributed to this knowledge, as a tracer of past bottom water provenance and mixing. Here, we extend the implementation of Nd isotopes in the physical-biogeochemical Bern3D model by revising a number of critical parameterizations, which result in an improved description of the marine Nd cycle. We exploit the dynamically consistent framework of the model, which allows us to assess the processes driving non-conservative Nd isotope behavior with a particular focus on the Last Glacial Maximum (LGM) and its substantially different climatic, oceanic, and biogeochemical boundary conditions. We show that the more radiogenic Nd isotopic compositions found throughout the glacial ocean can be explained by changes in the weathering input fluxes and do not require large reorganizations of the deep circulation. Our findings further highlight that the Nd isotopic composition of a water mass can not only be significantly affected by a benthic Nd flux, but also be modified by the vertical downward transport of Nd via reversible scavenging. While these non-conservative processes only have a limited impact in the modern ocean, they were substantially more pronounced during the LGM and mostly independent of the circulation state, with their contributions being non-linear, partially opposing, and spatially variable. During the transiently simulated deglaciation Nd isotope variations induced by major circulation weakenings and resumptions are found to be most pronounced in the South Atlantic, while they are increasingly muted towards the north. Hence, it emerges that the interpretation of authigenic Nd isotope records requires more spatially specific considerations of non-conservative processes in order to more reliably infer basin-scale ocean circulation and water mass mixing of the past.
    Type: Article , PeerReviewed
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  • 6
    Publication Date: 2024-02-07
    Description: The neodymium isotope composition (ɛNd) 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 ɛNd 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 ɛNd. 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 Nd. While the ɛNd of the Mn-oxide coated resin (−4.0) was similar to that of SoG seawater used for the incubation (−3.7), the Nd/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 Nd/Nd ratio of the Mn-oxide resin is necessary to determine the predominant source of Nd to the resin because the ɛNd 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 ɛNd 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 ɛNd 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 ɛNd in the authigenic phases of marine sediments.
    Type: Article , PeerReviewed
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  • 7
    Publication Date: 2024-02-07
    Description: Stable barium isotopes are a potential proxy for riverine inputs into the ocean that reflect monsoon variability and climate change. However, dissolved Ba isotope (δ138BaDBa) geochemistry in river estuaries, a dynamic land to ocean transition zone, has rarely been systematically examined to date. Here, we show that significant Ba isotope fractionation occurs at near-zero salinities in the Yangtze and Pearl River Estuary, whereas conservative mixing dominates δ138BaDBa distributions beyond low salinities, which are well predicted by an ion exchange model. Elevated δ138BaDBa in the river endmember results from preferential removal of light Ba isotopes by adsorption to fluvial particles. Subsequently, δ138BaDBa rapidly drops to minimum signatures at increased salinities indicating particle desorption of isotopically light Ba. Nevertheless, the apparently conservative δ138BaDBa-salinity relationship beyond the low-salinity minimum in both estuaries provides a modern calibration for using Ba isotopes as a proxy for paleosalinity and river water inputs into the ocean.
    Type: Article , PeerReviewed
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    Format: other
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  • 8
    Publication Date: 2024-02-07
    Description: The neodymium isotopic composition (εNd) of seawater is one of the most important geochemical tracers to investigate water mass provenance, which can also serve as a proxy to reconstruct past variations in ocean circulation. Nd isotopes have recently also been used to reconstruct past circulation changes in the Mediterranean Sea on different time scales. However, the modern seawater εNd dataset for the Mediterranean Sea, which these reconstructions are based on, is limited and up to now only 160 isotopic measurements are available for the entire basin. The lack of present-day data also limits our understanding of the processes controlling the Nd cycle and Nd isotopic distribution in this semi-enclosed basin. Here we present new εNd data from 24 depth profiles covering all Mediterranean sub-basins, which significantly increases the available dataset in the Mediterranean Sea. The main goal of our study is to better characterize the relationship between the dissolved Nd isotope distributions and major water masses in the Mediterranean Sea and to investigate the impact and relative importance of local non-conservative modifications, which include input of riverine particles and waters, aeolian-derived material and exchange with the sediments at continental margins. This comprehensive εNd dataset reveals a clear εNd – salinity correlation and a zonal and depth gradient with εNd systematically increasing from the western to the eastern Mediterranean basin (average εNd = −8.8 ± 0.8 and −6.7 ± 1 for the entire water column, respectively), reflecting the large-scale basin circulation. We have evaluated the conservative εNd behaviour in the Mediterranean Sea and quantified the non-conservative components of the εNd signatures by applying an Optimum Multiparameter (OMP) analysis and results from the Parametric Optimum Multiparameter (POMP) analysis of Jullion et al. (2017). The results of the present study combined with previously published Nd isotope values indicate that dissolved εNd behaves overall conservatively in the open Mediterranean Sea and show that its water masses are clearly distinguishable by their Nd isotope signature. However, misfits between measured and OMP- and POMP-derived εNd values exist in almost all sub-basins, especially in the eastern Levantine Basin and Alboran Sea at intermediate-deep depths, which can be explained by the influence of detrital lithogenic εNd signatures through interaction with highly radiogenic Nile sourced volcanic fractions and unradiogenic sediments, respectively. The radiogenic signature acquired in the eastern Levantine Basin is carried by the Levantine Intermediate Water and transferred conservatively to the entire Mediterranean at intermediate depths. Our measured εNd values and OMP- and POMP-derived results indicate that non-conservative contributions originating from sediment sources are then propagated by water mass circulation (with distinct preformed εNd) along the Mediterranean Sea through advection and conservative mixing. Mediterranean εNd effectively traces the mixing between the different water masses in this semi-enclosed basin and is a suitable water mass tracer.
    Type: Article , PeerReviewed
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  • 9
    Publication Date: 2024-02-07
    Description: The high latitude regions play a key role in regulating the marine biogeochemical cycling of barium (Ba) and the pre-formed Ba isotope compositions in the global ocean. In this study, we present 17 new depth profiles of dissolved Ba concentrations ([Ba]) and isotope compositions (δ138Ba) from the high latitude Atlantic, Pacific and Southern Oceans to trace the ventilation of deep waters in the Southern Ocean and their subsequent transport throughout the global ocean. Our data reveal how biogeochemical processes in the Southern Ocean generate distinct δ138Ba signatures of upper ocean water masses, and that large scale ocean circulation constrains the meridional gradient of δ138Ba distributions in the deep Atlantic Ocean. The significant increase in [Ba] of deep waters in the North Pacific is mainly achieved through dissolution of sinking particles which adds a δ138Ba signal comparable to the deep Pacific Ocean.
    Type: Article , PeerReviewed
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  • 10
    Publication Date: 2024-02-07
    Description: Reactive iron (Fe) oxides in marine sediments may represent a source of bioavailable Fe to the ocean via reductive dissolution and sedimentary Fe release or can promote organic carbon preservation and long-term burial. Furthermore, enrichments of reactive Fe (sum of Fe oxides, carbonates and sulfides normalized to total Fe) in ancient sediments are utilized as a paleo-proxy for anoxic conditions. Considering the general importance of reactive Fe oxides in marine biogeochemistry, it is important to quantify their terrestrial sources and fate at the land-ocean interface. We applied sequential Fe extractions to sediments from the Amazon shelf to investigate the transformation of river-derived Fe oxides during early diagenesis. We found that ∼22 % of the Amazon River-derived Fe oxides are converted to Fe-containing clay minerals in Amazon shelf sediments. The incorporation of reactive Fe into authigenic clay minerals (commonly referred to as reverse weathering) is substantiated by the relationship between Fe oxide loss and potassium (K) uptake from sedimentary pore waters, which is in agreement with the previously reported Fe/K stoichiometry of authigenic clay minerals. Mass balance calculations suggest that widely applied sequential extractions do not separate Fe-rich authigenic clay minerals from reactive Fe oxides and carbonates. We conclude that the balance between terrestrial supply of reactive Fe and reverse weathering in continental margin sediments has to be taken into account in the interpretation of sedimentary Fe speciation data. Key Points - Reactive Fe is transferred from river-derived Fe oxides into Fe-containing silicate minerals during early diagenesis - Standard sequential extraction schemes do not separate Fe oxides and carbonates from authigenic silicate minerals in Amazon shelf sediments - Terrigenous supply of reactive Fe and reverse weathering need to be considered in the interpretation of sedimentary Fe speciation
    Type: Article , PeerReviewed
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