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  • ddc:551.9  (7)
  • 1
    Publication Date: 2023-08-08
    Description: Many terrestrial silicate reservoirs display a characteristic depletion in Nb, which has been explained in some studies by the presence of reservoirs on Earth with superchondritic Nb/Ta. As one classical example, K-rich lavas from the Sunda rear-arc, Indonesia, have been invoked to tap such a high-Nb/Ta reservoir. To elucidate the petrogenetic processes active beneath the Java rear-arc and the causes for the superchondritic Nb/Ta in some of these lavas, we studied samples from the somewhat enigmatic Javanese rear-arc volcano Muria, which allow conclusions regarding the across-arc variations in volcanic output, source mineralogy and subduction components. We additionally report some data for an along-arc sequence of lavas from the Indonesian part of the Sunda arc, extending from Krakatoa in the west to the islands of Bali and Lombok in the east. We present major and trace element concentrations, Sr–Nd–Hf–Pb isotope compositions, and high-field-strength element (HFSE: Nb, Ta, Zr, Hf, W) concentrations obtained via isotope dilution and MC-ICP-MS analyses. The geochemical data are complemented by melting models covering different source compositions with slab melts formed at variable P–T conditions. The radiogenic isotope compositions of the frontal arc lavas in combination with their trace element systematics confirm previously established regional variations of subduction components along the arc. Melting models show a clear contribution of a sediment-derived component to the HFSE budget of the frontal arc lavas, particularly affecting Zr–Hf and W. In contrast, the K-rich rear-arc lavas tap more hybrid and enriched mantle sources. The HFSE budget of the rear-arc lavas is in particular characterized by superchondritic Nb/Ta (up to 25) that are attributed to deep melting involving overprint by slab melts formed from an enriched garnet–rutile-bearing eclogitic residue. Sub-arc slab melting was potentially triggered along a slab tear beneath the Sunda arc, which is the result of the forced subduction of an oceanic basement relief ~ 8 Myr ago as confirmed by geophysical studies. The purported age of the slab tear coincides with a paucity in arc volcanism, widespread thrusting of the Javanese basement crust as well as the short-lived nature of the K-rich rear-arc volcanism at that time.
    Description: Deutscher Akademischer Austauschdienst http://dx.doi.org/10.13039/501100001655
    Description: Gottfried Wilhelm Leibniz Universität Hannover (1038)
    Keywords: ddc:551.9 ; Rear-arc volcanism ; Superchondritic Nb/Ta ; Muria ; Sunda arc
    Language: English
    Type: doc-type:article
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  • 2
    Publication Date: 2023-11-18
    Description: Noble gases are important tracers of planetary accretion and acquisition of volatiles to planetary atmospheres and interiors. Earth’s mantle hosts solar-type helium and neon for which 〈sup〉20〈/sup〉Ne/〈sup〉22〈/sup〉Ne ratios advocate either incorporation of solar wind irradiated solids or solar nebula gas dissolution into an early magma ocean. However, the exact source location of primordial signatures remains unclear. Here we use high-resolution stepwise heating gas extraction experiments to analyse interior samples of the iron meteorite Washington County and find that they contain striking excesses of solar helium and neon. We infer that the Washington County protolith was irradiated by solar wind and that implanted noble gases were partitioned into segregating metal melts. The corollary that solar signatures are able to enter the cores of differentiated planetesimals and protoplanets validates hypotheses that Earth’s core may have incorporated solar noble gases and may be contributing to the solar signatures observed in Earth’s mantle.
    Description: Incorporation of iron meteorites in the core could explain variable noble gas signatures in different mantle reservoirs, according to stepwise heating experiments which show that the Washington County meteorite carries solar wind-derived He and Ne.
    Description: Klaus Tschira Stiftung (Klaus Tschira Foundation) https://doi.org/10.13039/501100007316
    Description: https://doi.org/10.26022/IEDA/111938
    Keywords: ddc:551.9 ; Core processes ; Early solar system ; Geochemistry ; Geodynamics ; Meteoritics
    Language: English
    Type: doc-type:article
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  • 3
    Publication Date: 2023-11-13
    Description: Ocean island basalts (OIB) show variable 〈sup〉182〈/sup〉W deficits that have been attributed to either early differentiation of the mantle or core‐mantle interaction. However, 〈sup〉182〈/sup〉W variations may also reflect nucleosynthetic isotope heterogeneity inherited from Earth's building material, which would be evident from correlated 〈sup〉182〈/sup〉W and 〈sup〉183〈/sup〉W anomalies. Some datasets for OIB indeed show hints for such correlated variations, meaning that a nucleosynthetic origin of W isotope anomalies in OIB cannot be excluded. We report high‐precision W isotope data for OIB from Samoa and Hawaii, which confirm previously reported 〈sup〉182〈/sup〉W deficits for these samples, but also demonstrate that none of these samples have resolvable 〈sup〉183〈/sup〉W anomalies. These data therefore rule out a nucleosynthetic origin of the 〈sup〉182〈/sup〉W deficits in OIB, which most likely reflect the entrainment of either core material or an overabundance of late‐accreted materials within OIB mantle sources. If these processes occurred over Earth's history, they may have also been responsible for shifting the 〈sup〉182〈/sup〉W composition of the bulk mantle to its modern‐day value. We also report Mo isotope data for some Hawaiian OIB, which reveal no resolved nucleosynthetic Mo isotopic anomalies. This is consistent with inheritance of 〈sup〉182〈/sup〉W deficits in OIB from the addition of either core or late‐accreted material, but only if these materials have a non‐carbonaceous (NC) meteorite‐like heritage. As such, these data rule out significant contributions of carbonaceous chondrite (CC)‐like materials to either Earth's core or late accretion.
    Description: Plain Language Summary: Some ocean island basalts (OIB) may contain a record of processes and characteristics of the deepest parts of Earth's mantle, including at the boundary between the iron‐rich core and mantle. Like some prior studies, we measured tungsten isotopes within OIB from Hawaii and Samoa, and report that tungsten isotopes in these OIB differ in their characteristics compared to what is observed in modern rocks that are most representative of the upper part of Earth's mantle. One explanation for these tungsten isotope anomalies is that they are a signature of chemical interaction between the core and lower mantle, suggesting that the core 'leaks' into the lower mantle. Another possibility proposed here is that these tungsten isotope anomalies reflect ancient crust that contained dense, meteorite‐like materials, which sank to the bottom of the mantle during Earth's early history. Using isotopes of another element, molybdenum, we show that the source(s) of these tungsten isotope anomalies do not contain a significant number of materials that originated from the outer Solar System before being added to Earth during its formation.
    Description: Key Points: 〈sup〉182〈/sup〉W deficits in ocean island basalts are confirmed, but correlated 〈sup〉182〈/sup〉W–〈sup〉183〈/sup〉W anomalies present in prior datasets are not confirmed. 〈sup〉182〈/sup〉W deficits may reflect core‐mantle interaction or an overabundance of late‐accreted materials, but not nucleosynthetic effects. Mo isotope data similar to BSE estimate; W‐Mo data rule out significant contribution of CC‐like material to Earth's core or late accretion.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: https://doi.org/10.35003/YCUKOX
    Keywords: ddc:551.9 ; core‐mantle interaction ; late accretion ; tungsten isotopes ; molybdenum isotopes ; ocean island basalts ; nucleosynthetic effects
    Language: English
    Type: doc-type:article
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  • 4
    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
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  • 5
    Publication Date: 2023-07-06
    Description: The accessories perovskite, pyrochlore, zirconolite, calzirtite and melanite from carbonatites and carbonate-rich foidites from the Kaiserstuhl are variously suited for the in situ determination of their U–Pb ages and Sr, Nd- and Hf-isotope ratios by LA-ICP-MS. The 143Nd/144Nd ratios may be determined precisely in all five phases, the 176Hf/177Hf ratios only in calzirtite and the 87Sr/86Sr ratios in perovskites and pyrochlores. The carbonatites and carbonate-rich foidites belong to one of the three magmatic groups that Schleicher et al. (1990) distinguished in the Kaiserstuhl on the basis of their Sr, Nd and Pb isotope ratios. Tephrites, phonolites and essexites (nepheline monzogabbros) form the second and limburgites (nepheline basanites) and olivine nephelinites the third. Our 87Sr/86Sr isotope data from the accessories overlap with the carbonatite and olivine nephelinite fields defined by Schleicher et al. (1990) but exhibit a much narrower range. These and the εNd and εHf values plot along the mantle array in the field of oceanic island basalts relatively close to mid-ocean ridge basalts. Previously reported K–Ar, Ar–Ar and fission track ages for the Kaiserstuhl lie between 16.2 and 17.8 Ma. They stem entirely from the geologically older tephrites, phonolites and essexites. No ages existed so far for the geologically younger carbonatites and carbonate-rich foidites except for one apatite fission track age (15.8 Ma). We obtained precise U–Pb ages for zirconolites and calzirtites of 15.66, respectively 15.5 Ma (± 0.1 2σ) and for pyrochlores of 15.35 ± 0.24 Ma. Only the perovskites from the Badberg soevite yielded a U–P concordia age of 14.56 ± 0.86 Ma while the perovskites from bergalites (haüyne melilitites) only gave 206Pb/238U and 208Pb/232Th ages of 15.26 ± 0.21, respectively, 15.28 ± 0.48 Ma. The main Kaiserstuhl rock types were emplaced over a time span of 1.6 Ma almost 1 million years before the carbonatites and carbonate-rich foidites. These were emplaced within only 0.32 Ma.
    Description: Frankfurt Institute for Advanced Studies (FIAS) (4401)
    Keywords: ddc:551.9 ; In situ determination of Sr, Nd and Hf isotope ratios ; In situ determination of U–Pb ages ; Accessories in carbonatites ; Kaiserstuhl
    Language: English
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  • 6
    Publication Date: 2023-07-20
    Description: Volatiles released from magma can form bubbles and leave the magma body to eventually mix with atmospheric air. The composition of those volatiles, as derived from measurements made after their emission, is used to draw conclusions on processes in the Earth's interior or their influences on Earth's atmosphere. So far, the discussion of the influence of high‐temperature mixing with atmospheric air (in particular oxygen) on the measured volcanic gas composition is almost exclusively based on thermodynamic equilibrium (TE) considerations. By modeling the combined effects of C‐H‐O‐S reaction kinetics, turbulent mixing, and associated cooling during the first seconds after magmatic gas release into the atmosphere we show that the resulting gas compositions generally do not represent TE states, with individual species (e.g., CO, H2, H2S, OCS, SO3, HO2, H2O2) deviating by orders of magnitude from equilibrium levels. Besides revealing the chemical details of high‐temperature emission processes, our results question common interpretations of volcanic gas studies, particularly affecting the present understanding of auto‐catalytic conversion of volcanic halogen species in the atmosphere and redox state determination from volcanic plume gas measurements.
    Description: Plain Language Summary: A major fraction of magmatic gas emissions are released into the atmosphere from open vents. The emission processes are characterized by fast turbulent mixing with atmospheric air (within seconds) and associated rapid cooling. Hardly anything is known about the chemical kinetics within this brief mixing and cooling period. We simulate the chemical kinetics during the first seconds of hot magmatic gases in the atmosphere and find severe deviation to common interpretations and central thermodynamic equilibrium assumptions prevailing in volcanic gas geochemistry.
    Description: Key Points: We model the chemical kinetics of high‐temperature volcanic gas emissions within the first seconds of mixing with atmospheric air. We identify key chemical processes within the magma‐atmosphere interface and quantify influences on the volcanic plume composition. Our results question common assumptions prevailing in volcanic gas geochemistry and refine interpretations of gas emissions from open vents.
    Description: German Research Foundation
    Keywords: ddc:551.9 ; volcanic gas emissions ; kinetic chemistry modeling ; atmospheric chemistry ; magmatic redox states ; reactive halogen chemistry
    Language: English
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  • 7
    Publication Date: 2023-06-19
    Description: Geochemical analyses of carbonate minerals yield multiple parameters which can be used to estimate the temperature and water composition at which they formed. Analysis of fluid trapped in minerals is a potentially powerful tool to reconstruct paleotemperatures as well as diagenetic and hydrothermal processes, as these could represent the parent fluid. Internal fluids play important roles during the alteration of carbonate fossils, lowering energetic barriers associated with resetting of clumped isotopes, as well as mediating the transport of elements during diagenesis. Here, we explore the behavior of the ∆47–∆48 “dual‐clumped” isotope thermometer during fluid‐carbonate interaction and demonstrate that it is highly sensitive to the water/carbonate ratio, behaving as a linear system in “rock buffered” alteration, and as a decoupled system in water‐dominated systems due to non‐linear mixing effects in ∆48. Dry heating experiments show that the extrapolated “heated” end‐member is indistinguishable from the predicted ∆47 and ∆48 value expected for the experimental temperature. Furthermore, we evaluate two common laboratory sampling methods for their ability to thermally alter samples. We find that the temperature of the commonly used crushing cells used to vapourize water for fluid inclusion δ18O analyses is insufficient to cause fluid‐carbonate oxygen isotope exchange, demonstrating its suitability for analyses of fluid inclusions in carbonates. We also find that belemnites sampled with a hand‐drill yield significantly warmer paleotemperatures than those sampled with mortar and pestle. We conclude that thermally‐driven internal fluid‐carbonate exchange occurs indistinguishably from isotopic equilibrium, limited by the extent to which internal water and carbonate can react.
    Description: Plain Language Summary: Carbonate minerals contain multiple, independent, chemical and isotopic parameters which can be used to calculate the temperature at which the mineral formed. If these proxies agree with one another, it has been confidently assumed that the temperature is indeed genuine. Here, we investigate three such parameters and show how they record kinetic processes during mineral formation, as well as thermally‐driven processes which may alter a climate record. We find that this method could potentially be used to study the kinetic factors at play during biomineralization, even if the “true” temperature is unknown. We also find that some thermal processes result in all three parameters agreeing with one another. Because thermal alteration poses a potential dilemma for climate researchers, we investigate two common laboratory preparation techniques that involve heating a sample before analysis: drilling and heating sample for fluid inclusion analysis. We find that the heat of a drill is sufficient to facilitate these reactions, and potentially imparts a warm bias onto paleotemperatures, however the apparatus used for analyzing fluid inclusions does not appear to significantly alter the material. We conclude our approach using fluid inclusion analysis and dual‐clumped isotopes has the potential to resolve many ambiguities in interpreting climate records.
    Description: Key Points: We explore the behavior of dual‐clumped and fluid‐inclusion isotope paleothermometers during thermal alteration. Different conditions during diagenesis may result in discrepant paleotemperature estimates, which may be used to identify altered records. Hand‐drilling belemnites produces sufficient heat to reset paleotemperatures, but the heat during analysis of fluid inclusions does not.
    Description: DFG
    Description: https://doi.org/10.5281/zenodo.7565557
    Keywords: ddc:551.9 ; diagenesis ; clumped isotopes ; fluid inclusions ; numerical modeling
    Language: English
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