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  • 1
    Publication Date: 2022-12-07
    Description: The radiogenic isotope heterogeneity of oceanic basalts is often assessed using 2D isotope ratio diagrams. But because the underlying data are at least six dimensional (87Sr/86Sr, 143Nd/144Nd, 176Hf/177Hf, and 208,207,206Pb/204Pb), it is important to examine isotopic affinities in multi‐dimensional data space. Here, we apply t‐distributed stochastic neighbor embedding (t‐SNE), a multi‐variate statistical data analysis technique, to a recent compilation of radiogenic isotope data of mid ocean ridge (MORB) and ocean island basalts (OIB). The t‐SNE results show that the apparent overlap of MORB‐OIB data trends in 2‐3D isotope ratios diagrams does not exist in multi‐dimensional isotope data space, revealing that there is no discrete “component” that is common to most MORB‐OIB mantle sources on a global scale. Rather, MORB‐OIB sample stochastically distributed small‐scale isotopic heterogeneities. Yet, oceanic basalts with the same isotopic affinity, as identified by t‐SNE, delineate several globally distributed regional domains. In the regional geodynamic context, the isotopic affinity of MORB and OIB is caused by capturing of actively upwelling mantle by adjacent ridges, and thus melting of mantle with similar origin in on, near, and off‐ridge settings. Moreover, within a given isotopic domain, subsidiary upwellings rising from a common deep mantle root often feed OIB volcanism over large surface areas. Overall, the t‐SNE results define a fundamentally new basis for relating isotopic variations in oceanic basalts to mantle geodynamics, and may launch a 21st century era of “chemical geodynamics.”
    Description: Plain Language Summary: The isotopic heterogeneity of basalts erupted at mid ocean ridges (MORB) and ocean islands (OIB) reflects the chemical evolution of Earth's mantle. The visual inspection of various 2D isotope ratio diagrams has fueled a four decade‐long discussion whether basalt heterogeneity reflects melting of only a small number of mantle components, and in particular, whether the apparent overlap of local data trends in global 2D isotope ratio diagrams indicates that melting of a common mantle component contributes to most MORB‐OIB. Here, we use multi‐variate statistical data analysis to show that the apparent overlap of MORB‐OIB data trends in 2D isotope ratio diagrams does not exist in multi‐dimensional isotope data space. Our finding invalidates any inference made for mantle compositional evolution based on the previously proposed existence of a common mantle component, its potential nature or distribution within the mantle. Rather, global MORB‐OIB sample small‐scale isotopic heterogeneities that are distributed stochastically in the Earth's mantle. Yet, MORB‐OIB with the same isotopic affinity, as identified by our multi‐variate data analysis, delineate several globally distributed regional domains. Within the regional geodynamic context, this discovery forms a fundamentally new basis for relating isotopic variations in MORB‐OIB to mantle geodynamics.
    Description: Key Points: Multi‐variate statistical data analysis (t‐distributed stochastic neighbor embedding) identifies global Sr‐Nd‐Hf‐Pb isotopic affinities of oceanic basalts. There is no “common mantle component;” rather, global mid ocean ridge‐ocean island basalts sample stochastically distributed small‐scale isotopic heterogeneities. Globally distributed regional domains of isotopically alike oceanic lavas define a new basis for relating isotopic variations to geodynamics.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung http://dx.doi.org/10.13039/501100001711
    Description: DAAD, German Academic Exchange Service
    Description: https://doi.org/10.25625/0SVW6S
    Description: https://doi.org/10.25625/BQENGN
    Keywords: ddc:551.9 ; mantle heterogeneity ; MORB ; OIB ; geodynamics ; t‐SNE ; radiogenic isotopes ; machine learning
    Language: English
    Type: doc-type:article
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  • 2
    Publication Date: 2022-11-28
    Description: Mass fractions of Cu, Zn, Ga, Ag, Cd, In, Sn and Tl were determined via isotope dilution quadrupole ICP-MS in twenty-one geological reference materials (RMs) and the carbonaceous chondrites Orgueil (CI1), Murchison (CM2) and Allende (CV3). The RMs comprise basaltic/mafic (BCR-2, BE-N, BHVO-1, BHVO-2, BIR-1, BRP-1, JB-2, OKUM, W-2, WS-E), intermediate/felsic (AGV-2, G-2, JA-2, RGM-1), ultramafic (DTS-2b, MUH-1, PCC-1, UB-N) and sedimentary (MAG-1, OU-6) rocks. Pressure digestion was applied for nonbasaltic samples to ensure effective sample digestion. For basaltic RMs, hot plate digestion was found to be sufficient for a quantitative recovery of the target elements. To minimise interferences and increase ion beam intensities during isotope ratio analyses by ICP-MS, separation of the target elements was carried out from single sample aliquots using a novel anion exchange procedure. The intermediate precision (2s) estimated from two to four replicate analyses was usually 〈 4% and results are in agreement with literature data, where available. Especially for Ag and Tl, the intermediate precision was compromised, likely due to low ion beam intensities and, hence, higher background and blank contributions. For ultramafic RMs, nugget effects and incomplete digestion might compromise the intermediate precision. Results for the carbonaceous chondrites Orgueil (CI1), Murchison (CM2) and Allende (CV3) agree well with previously reported data.
    Keywords: ddc:551.9 ; isotope dilution ; chalcophile elements ; geological reference materials ; chondrites ; Q-ICP-MS
    Language: English
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  • 3
    Publication Date: 2022-10-19
    Description: Key Points: Literature review of 7200 geoanalytical publications for the year 2020. 628 selected articles with summaries of target analytes, relevant reference materials and producers. Selected publications include data obtained by new analytical developments and improved analytical protocols for established RMs, and identifies recently developed RMs for specific scientific topics. image
    Description: This bibliographic review gives an overview of scientific publications in 2020 that contribute important data for geoanalytical reference materials (RMs).
    Keywords: ddc:551.9
    Language: English
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  • 4
    Publication Date: 2022-10-12
    Description: Large bell‐shaped calcite formations called “Hells Bells” were discovered underwater in the stratified cenote El Zapote on the Yucatán Peninsula, Mexico. Together with these extraordinary speleothems, divers found a white, cloudy turbid layer into which some Hells Bells partially extend. Here, we address the central question if the formation of the turbid layer could be based on microbial activity, more specifically, on microbially induced calcite precipitation. Metagenomic and metatranscriptomic profiling of the microbial community in the turbid layer, which overlaps with the pelagic redoxcline in the cenote, revealed chemolithoautotrophic Hydrogenophilales and unclassified β‐Proteobacteria as the metabolic key players. Bioinformatic and hydrogeochemical data suggest chemolithoautotrophic oxidation of sulfide to zero‐valent sulfur catalyzed by denitrifying organisms due to oxygen deficiency. Incomplete sulfide oxidation via nitrate reduction and chemolithoautotrophy are both proton‐consuming processes, which increase the pH in the redoxcline favoring authigenic calcite precipitation and may contribute to Hells Bells growth. The observed mechanism of microbially induced calcite precipitation is potentially applicable to many other stagnant sulfate‐rich water bodies.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: CONACYT‐FONCICYT‐DADC
    Description: https://doi.org/10.11588/data/TMYLWS
    Description: https://doi.org/10.11588/data/GYLDH5
    Keywords: ddc:551.9
    Language: English
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  • 5
    Publication Date: 2022-10-04
    Description: Rapid and profound climatic and environmental changes have been predicted for the Antarctic Peninsula with so far unknown impact on the biogeochemistry of the continental shelves. In this study, we investigate benthic carbon sedimentation, remineralization and iron cycling using sediment cores retrieved on a 400 mile transect with contrasting sea ice conditions along the eastern shelf of the Antarctic Peninsula. Sediments at comparable water depths of 330–450 m showed sedimentation and remineralization rates of organic carbon, ranging from 2.5 to 13 and 1.8–7.2 mmol C m−2 d−1, respectively. Both rates were positively correlated with the occurrence of marginal sea ice conditions (5%–35% ice cover) along the transect, suggesting a favorable influence of the corresponding light regime and water column stratification on algae growth and sedimentation rates. From south to north, the burial efficiency of organic carbon decreased from 58% to 27%, while bottom water temperatures increased from −1.9 to −0.1°C. Net iron reduction rates, as estimated from pore‐water profiles of dissolved iron, were significantly correlated with carbon degradation rates and contributed 0.7%–1.2% to the total organic carbon remineralization. Tightly coupled phosphate‐iron recycling was indicated by significant covariation of dissolved iron and phosphate concentrations, which almost consistently exhibited P/Fe flux ratios of 0.26. Iron efflux into bottom waters of 0.6–4.5 μmol Fe m−2 d−1 was estimated from an empirical model. Despite the deep shelf waters, a clear bentho‐pelagic coupling is indicated, shaped by the extent and duration of marginal sea ice conditions during summer, and likely to be affected by future climate change.
    Description: Plain Language Summary: The seafloor of the shallow shelf seas plays a significant role in the recycling of organic carbon and acts as a nutrient source for algae growth in the upper water layers. In Antarctic waters, the change in sea ice cover has a great impact on the growth of algae and the subsequent sinking of organic carbon to the seafloor. With global warming, profound changes in sea ice cover are expected for the Antarctic Peninsula. To better understand its imprint on the seafloor, we collected sediment samples from different locations along the eastern shelf of the Antarctic Peninsula and measured how changes in sea ice cover influence the accumulation and recycling of organic carbon. We found that moderate sea ice cover of 5%–35% increases the amount of organic carbon received by the seafloor and that the fraction that is buried in the sediments decreases from south (58%) to north (27%). We further measured that more iron, an important micro‐nutrient for algae growth, can be released from the seafloor the more organic carbon accumulates. Thus, sea ice conditions determine the organic carbon accumulation, turnover, and nutrient release at the seafloor, which are likely to be affected by future climate change.
    Description: Key Points: Antarctic shelf sediments underlying marginal sea ice cover exhibit high sedimentation and remineralization rates of organic carbon. A high degree of sedimentary Fe‐recycling is found which scales with organic carbon remineralization rates. Coupling between P and Fe recycling is observed with a constant P/Fe flux ratio of 0.26 for sediments with high Fe and P recycling rates.
    Description: Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research http://dx.doi.org/10.13039/501100003207
    Description: https://doi.org/10.1594/PANGAEA.942455
    Keywords: ddc:551.9
    Language: English
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  • 6
    Publication Date: 2022-10-04
    Description: The Arctic Ocean is considered a source of micronutrients to the Nordic Seas and the North Atlantic Ocean through the gateway of Fram Strait (FS). However, there is a paucity of trace element data from across the Arctic Ocean gateways, and so it remains unclear how Arctic and North Atlantic exchange shapes micronutrient availability in the two ocean basins. In 2015 and 2016, GEOTRACES cruises sampled the Barents Sea Opening (GN04, 2015) and FS (GN05, 2016) for dissolved iron (dFe), manganese (dMn), cobalt (dCo), nickel (dNi), copper (dCu) and zinc (dZn). Together with the most recent synopsis of Arctic‐Atlantic volume fluxes, the observed trace element distributions suggest that FS is the most important gateway for Arctic‐Atlantic dissolved micronutrient exchange as a consequence of Intermediate and Deep Water transport. Combining fluxes from FS and the Barents Sea Opening with estimates for Davis Strait (GN02, 2015) suggests an annual net southward flux of 2.7 ± 2.4 Gg·a−1 dFe, 0.3 ± 0.3 Gg·a−1 dCo, 15.0 ± 12.5 Gg·a−1 dNi and 14.2 ± 6.9 Gg·a−1 dCu from the Arctic toward the North Atlantic Ocean. Arctic‐Atlantic exchange of dMn and dZn were more balanced, with a net southbound flux of 2.8 ± 4.7 Gg·a−1 dMn and a net northbound flux of 3.0 ± 7.3 Gg·a−1 dZn. Our results suggest that ongoing changes to shelf inputs and sea ice dynamics in the Arctic, especially in Siberian shelf regions, affect micronutrient availability in FS and the high latitude North Atlantic Ocean.
    Description: Plain Language Summary: Recent studies have proposed that the Arctic Ocean is a source of micronutrients such as dissolved iron (dFe), manganese (dMn), cobalt (dCo), nickel (dNi), copper (dCu) and zinc (dZn) to the North Atlantic Ocean. However, data at the Arctic Ocean gateways including Fram Strait and the Barents Sea Opening have been missing to date and so the extent of Arctic micronutrient transport toward the Atlantic Ocean remains unquantified. Here, we show that Fram Strait is the most important gateway for Arctic‐Atlantic micronutrient exchange which is a result of deep water transport at depths 〉500 m. Combined with a flux estimate for Davis Strait, this study suggests that the Arctic Ocean is a net source of dFe, dNi and dCu, and possibly also dCo, toward the North Atlantic Ocean. Arctic‐Atlantic dMn and dZn exchange seems more balanced. Properties in the East Greenland Current showed substantial similarities to observations in the upstream Central Arctic Ocean, indicating that Fram Strait may export micronutrients from Siberian riverine discharge and shelf sediments 〉3,000 km away. Increasing Arctic river discharge, permafrost thaw and coastal erosion, all consequences of ongoing climate change, may therefore alter future Arctic Ocean micronutrient transport to the North Atlantic Ocean.
    Description: Key Points: Fram Strait is the major gateway for Arctic‐Atlantic exchange of the dissolved micronutrients Fe, Mn, Co, Ni, Cu and Zn. The Arctic is a net source of dissolved Fe, Co, Ni and Cu to the Nordic Seas and toward the North Atlantic; Mn and Zn exchange are balanced. Waters of the Central Arctic Ocean, including the Transpolar Drift, are the main drivers of gross Arctic micronutrient export.
    Description: German Research Foundation
    Description: Netherlands Organization for Scientific Research
    Description: https://doi.pangaea.de/10.1594/PANGAEA.859558
    Description: https://doi.pangaea.de/10.1594/PANGAEA.871030
    Description: https://doi.pangaea.de/10.1594/PANGAEA.868396
    Description: https://doi.pangaea.de/10.1594/PANGAEA.905347
    Description: https://dataportal.nioz.nl/doi/10.25850/nioz/7b.b.jc
    Description: https://doi.pangaea.de/10.1594/PANGAEA.933431
    Description: https://www.bco-dmo.org/dataset/718440
    Description: https://doi.org/10.1594/PANGAEA.936029
    Description: https://doi.org/10.1594/PANGAEA.936027
    Description: https://doi.pangaea.de/10.1594/PANGAEA.927429
    Keywords: ddc:551.9
    Language: English
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  • 7
    Publication Date: 2022-10-01
    Description: Internal water in cold‐water and tropical coral skeletons was extracted and measured for its oxygen and hydrogen isotope ratios. Water was extracted by crushing pieces of coral hard tissue in a percussion device connected to either a cavity ring‐down spectroscopy (CRDS) system or an isotope ratio mass spectrometry (IRMS) system. Despite most samples yielding sufficient water, each analytical system produces distinct isotope patterns. Experiments show that several characteristics specific to biominerals give rise to discrepancies and analytical artefacts that preclude the acquisition of reproducible isotope data. The main complication is that internal water in biogenic carbonates is distributed in an open interconnected micro‐network that readily exchanges with external water and potentially facilitates interaction with hydration water in the finely dispersed organic matrix in the coral skeleton. Furthermore, only an isotopically fractionated part of the internal water is released from the coral skeletons upon crushing. Altogether, isotope ratio measurement of internal water in corals with bulk crushing techniques does not give primary fluid isotope ratios useful for (palaeo‐)environmental or microbiological studies. As the resulting isotope patterns can show systematic behaviour per technique, isotope data may be erroneously interpreted to reflect the original calcifying fluid when using only a single technique to isotopically characterise internal fluids in coral skeletons.
    Description: Key Points: Free water trapped inside coral skeletons was extracted and isotopically analyzed on two commonly used techniques for fluid inclusion isotope analysis. Measured oxygen and hydrogen isotope ratios do not reproduce between the techniques due to several analytical artefacts. The water extracted from coral skeletons is not of primary origin.
    Description: Nederlandse Organisatie voor Wetenschappelijk Onderzoek http://dx.doi.org/10.13039/501100003246
    Description: Western Indian Ocean Marine Science Association http://dx.doi.org/10.13039/501100009106
    Keywords: ddc:551.9
    Language: English
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  • 8
    Publication Date: 2022-09-27
    Description: Little research attention has been given to validating clusters obtained from the groundwater geochemistry of the waterworks' capture zone with a prevailing lake‐groundwater exchange. To address this knowledge gap, we proposed a new scheme whereby Gaussian finite mixture modeling (GFMM) and Spike‐and‐Slab Bayesian (SSB) algorithms were utilized to cluster the groundwater geochemistry while quantifying the probability of the resulting cluster membership against each other. We applied GFMM and SSB to 13 geochemical parameters collected during different sampling periods at 13 observation points across the Barnim Highlands plateau located in the northeast of Berlin, Germany; this included 10 observation wells, two lakes, and a gallery of drinking production wells. The cluster analysis of GFMM yielded nine clusters, either with a probability ≥0.8, while the SSB produced three hierarchical clusters with a probability of cluster membership varying from 〈0.2 to 〉0.8. The findings demonstrated that the clustering results of GFMM were in good agreement with the classification as per the principal component analysis and Piper diagram. By superimposing the parameter clustering onto the observation clustering, we could identify discrepancies that exist among the parameters of a certain cluster. This enables the identification of different factors that may control the geochemistry of a certain cluster, although parameters of that cluster share a strong similarity. The GFMM results have shown that from 2002, there has been active groundwater inflow from the lakes towards the capture zone. This means that it is necessary to adopt appropriate measures to reverse the inflow towards the lakes.
    Description: Article impact statement: The probability of cluster membership quantified using an algorithm should be validated against another probabilistic‐based classifier.
    Description: Federal Ministry of Education and Research http://dx.doi.org/10.13039/501100002347
    Keywords: ddc:551.9 ; ddc:551.49
    Language: English
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  • 9
    Publication Date: 2022-08-09
    Description: Abundant volcanic activity occurs in the back‐arc region of the northern Tofua island arc where the Northeast Lau Spreading Center (NELSC) propagates southwards into older crust causing the formation of numerous seamounts at the propagating rift tip. An off‐axis volcanic diagonal ridge (DR) occurs at the eastern flank of the NELSC, linking the large rear‐arc volcano Niuatahi with the NELSC. New geochemical data from the NELSC, the southern propagator seamounts, and DR reveal that the NELSC lavas are tholeiitic basalts whereas the rear‐arc volcanoes typically erupt lavas with boninitic composition. The sharp geochemical boundary probably reflects the viscosity contrast between off‐axis hydrous harzburgitic mantle and dry fertile mantle beneath the NELSC. The new data do not indicate an inflow of Samoa plume mantle into the NELSC, confirming previously published He isotope data. The NELSC magmas form by mixing of an enriched and a depleted Indian Ocean‐type upper mantle end‐member implying a highly heterogeneous upper mantle composition in this area. Most NELSC lavas are little affected by a slab component implying that melting is adiabatic beneath the spreading center. The DR lavas show the influence of a component from the subducted Louisville Seamount Chain, which was previously thought to be restricted to the nearby arc volcanoes Niuatoputapu and Tafahi. This signature is rarely detected along the NELSC implying little mixing of melts from the low‐viscosity hydrous portion of the mantle wedge beneath the rear‐arc volcanoes into the melting region of the dry mantle beneath the NELSC.
    Description: Plain Language Summary: Volcanic activity is abundant at subduction zones and the chemical analysis of the erupted rocks allows to determine the material transport in the Earth's mantle. The Northeast Lau Spreading Center (NELSC) forms by extension and volcanism behind the northern Tofua island arc. Several large volcanic structures occur east of the NELSC and the lavas of these off‐axis volcanoes are chemically and isotopically distinct implying little mixing with the magmas of the NELSC. The differences suggest decompression melting of relatively dry mantle beneath the NELSC whereas the off‐axis volcanoes reflect melting of water‐rich mantle affected by fluids from the subducting Pacific Plate. The sharp geochemical boundary between the NELSC and off‐axis volcanoes is probably due to a large viscosity contrast between hydrous harzburgitic mantle and dry fertile mantle. Element and isotope ratios indicate that the NELSC magmas form by mixing of enriched and depleted portions of the upper mantle, and we do not find evidence for inflow of the Samoa deep mantle plume from the north. Some of the off‐axis lavas contain a component from a volcanic chain that was subducted some 4 million years ago and that was previously only known in two volcanoes of the Tofua island arc.
    Description: Key Points: Variably enriched mantle sources melt beneath the Northeast Lau Spreading Center (NELSC) but there is no evidence for Samoa mantle plume inflow. Relatively dry fertile mantle beneath NELSC causes sharp geochemical boundary with hydrous harzburgitic North Tonga mantle wedge. Subducted Louisville Seamount Chain material affects rear‐arc volcanism.
    Description: Bundesministerium für Bildung und Forschung (BMBF) http://dx.doi.org/10.13039/501100002347
    Description: Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/501100001659
    Keywords: ddc:551.21 ; ddc:551.116 ; ddc:551.9
    Language: English
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  • 10
    Publication Date: 2022-08-04
    Description: Due to their availability, low cost, nontoxicity, and tunability, polymeric carbon nitrides (CNx) represent one of the most attractive materials classes for the development of fully sustainable photo(electro)catalytic systems for solar‐driven water splitting. However, the development of CNx‐based photoanodes for visible light‐driven water oxidation to dioxygen is rather challenging, particularly due to issues related to photoelectrode stability and effective coupling of the light absorber with water oxidation catalysts. Herein, a triadic photoanode comprising a porous TiO2 electron collector scaffold sensitized by CNx coupled to a molecular cobalt polyoxometalate (CoPOM = [Co4(H2O)2(PW9O34)2]10) catalyst is reported. Complete water oxidation to dioxygen under visible (λ 〉 420 nm) light irradiation is demonstrated, with photocurrents down to relatively low bias potentials (0.2 V vs RHE). Furthermore, polyethyleneimine (PEI), a cationic polymer is shown to act as an effective and non‐sacrificial electrostatic linker for immobilization of the anionic CoPOM onto the negatively charged surface of CNx. The optimized deposition of CoPOM using the PEI linker translates directly into improved efficiency of the transfer of photogenerated holes to water molecules and to enhanced oxygen evolution. This work thus provides important design rules for effective immobilization of POM‐based catalysts into soft‐matter photoelectrocatalytic architectures for light‐driven water oxidation.
    Description: A triadic photoanode comprised of a porous TiO2 electron collector scaffold sensitized by polymeric carbon nitride and coupled to a molecular cobalt polyoxometalate (CoPOM) catalyst exhibits visible (λ 〉 420 nm) light‐driven water oxidation to dioxygen. The beneficial role of the cationic polyethyleneimine polymer as an effective electrostatic linker for immobilization of CoPOM onto carbon nitride is highlighted.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: Vector Stiftung http://dx.doi.org/10.13039/501100013912
    Keywords: ddc:551.9
    Language: English
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