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  • 551  (12)
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  • 1
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    Fluid/rock interaction and mass transfer in continental subduction zones: constraints from trace elements and isotopes (Li, B, O, Sr, Nd, Pb) in UHP rocks from the Chinese Continental Scientific Drilling Program, Sulu, East China (2018)
    Springer-Verlag | Berlin/Heidelberg
    Details
    Publication Date: 2021-03-29
    Description: In order to better understand the role of fluids during subduction and subsequent exhumation, we have investigated whole-rock and mineral chemistry (major and trace elements) and Li, B as well as O, Sr, Nd, Pb isotopes on selected continuous drill-core profiles through contrasting lithological boundaries from the Chinese Continental Scientific Drilling Program (CCSD) in Sulu, China. Four carefully selected sample sets have been chosen to investigate geochemical changes as a result of fluid mobilization during dehydration, peak metamorphism, and exhumation of deeply subducted continental crust. Our data reveal that while O and Sr-Nd-Pb isotopic compositions remain more or less unchanged, significant Li and/or B isotope fractionations occur between different lithologies that are in close contact during various metamorphic stages. Samples that are supposed to represent prograde dehydration as indicated by veins formed at high pressures (HP) are characterized by element patterns of highly fluid-mobile elements in the veins that are complementary to those of the host eclogite. A second sample set represents a UHP metamorphic crustal eclogite that is separated from a garnet peridotite by a thin transitional interface. Garnet peridotite and eclogite are characterized by a 〉10% difference in MgO, which, together with the presence of abundant hydroxyl-bearing minerals and compositionally different clinopyroxene grains demonstrate that both rocks have been derived from different sources that have been tectonically juxtaposed during subduction, and that hydrous silicate-rich fluids have been added from the subducting slab to the mantle. Two additional sample sets, comprising retrograde amphibolite and relatively fresh eclogite, demonstrate that besides external fluids, internal fluids can be responsible for the formation of amphibolite. Li and B concentrations and isotopic compositions point to losses and isotopic fractionation during progressive dehydration. On the other hand, fluids with isotopically heavier Li and B are added during retrogression. On a small scale, mantle-derived rocks may be significantly metasomatized by fluids derived from the subducted slab. Our study indicates that during high-grade metamorphism, Li and B may show different patterns of enrichment and of isotopic fractionation.
    Keywords: Fluid/rock interaction; Elemental transfer; Isotopic fractionation; Subduction and exhumation; Sulu ; 551 ; Earth Sciences; Mineralogy; Mineral Resources; Geology
    Language: English
    Type: article , publishedVersion
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  • 2
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    Chaotic three-dimensional distribution of Ba, Rb, and Sr in feldspar megacrysts grown in an open magmatic system (2018)
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    Publication Date: 2021-03-29
    Description: As has been demonstrated in recent years, the heterogeneities of coeval magmas can be more successfully revealed by zoned megacrysts rather than by analysis of the whole rocks hosting them. Here, the geochemical heterogeneities of feldspar megacrysts from the Karkonosze granite, Poland, are investigated by LA-ICP-MS. The crystals are the product of migration and growth in regions of poorly mixed magmas. 3D-modeling of the Ba, Sr, and Rb distributions emphasizes the importance of micro-domain growth morphologies. Two models of element behavior—a relative concentration model and a composition gradient model—provide a potentially effective tool for tracking the mixing process on a microscale. Measured concentrations of elements of different mobilities do not agree with what might be expected from the mixing of two end-member magmas. If mixing was the only process occurring, linear correlations between the concentrations of any two elements should be observed; this, however, is not the case. For combinations of any two of the three elements, modeling reveals differing non-linear correlations between concentrations. The megacryst heterogeneities provide an insight into how mixing magmas are chaotically advected to growing crystals and the degree of inter-magma element exchange between the magmas.
    Keywords: Mixing; Element mobility; Diffusion; Alkali feldspar; 3D-depiction; Cut-off value models; Gradient models; Probabilistic models; Geochemical heterogeneity; Karkonosze granite ; 551
    Language: English
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  • 3
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    Assessing the utility of trace and rare earth elements as biosignatures in microbial iron oxyhydroxides (2018)
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    Publication Date: 2021-03-29
    Description: Microbial iron oxyhydroxides are common deposits in natural waters, recent sediments, and mine drainage systems. Along with these minerals, trace and rare earth elements (TREE) are being accumulated within the mineralizing microbial mats. TREE patterns are widely used to characterize minerals and rocks, and to elucidate their evolution and origin. However, whether and which characteristic TREE signatures distinguish between a biological and an abiological origin of iron minerals is still not well-understood. Here we report on long-term flow reactor studies performed in the Tunnel of Äspö (Äspö Hard Rock Laboratory, Sweden). The development of microbial mats dominated by iron-oxidizing bacteria (FeOB), namely Mariprofundus sp. and Gallionella sp were investigated. The feeder fluids of the flow reactors were tapped at 183 and 290 m below sea-level from two brackish, but chemically different aquifers within the surrounding, ~1.8 Ga old, granodioritic rocks. The experiments investigated the accumulation and fractionation of TREE under controlled conditions of the subsurface continental biosphere, and enabled us to assess potential biosignatures evolving within the microbial iron oxyhydroxides. After 2 and 9 months, concentrations of Be, Y, Zn, Zr, Hf, W, Th, Pb, and U in the microbial mats were 103- to 105-fold higher than in the feeder fluids whereas the rare earth elements and Y (REE+Y) contents were 104- and 106-fold enriched. Except for a hydrothermally induced Eu anomaly, the normalized REE+Y patterns of the microbial iron oxyhydroxides were very similar to published REE+Y distributions of Archaean Banded Iron Formations (BIFs). The microbial iron oxyhydroxides from the flow reactors were compared to iron oxyhydroxides that were artificially precipitated from the same feeder fluid. Remarkably, these abiotic and inorganic iron oxyhydroxides show the same REE+Y distribution patterns. Our results indicate that the REE+Y mirror closely the water chemistry, but they do not allow to distinguish microbially mediated from inorganic iron precipitates. Likewise, all TREE studied showed an overall similar fractionation behavior in biogenic, abiotic, and inorganic iron oxyhydroxides. Exceptions are Ni and Tl, which were only accumulated in the microbial iron oxyhydroxides and may point to a potential utility of these elements as microbial biosignatures.
    Keywords: biosignatures; microbialmats; microbialironoxides; traceelements; rareearthelements; microbe–metalinteraction; bandedironformation ; 551
    Language: English
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  • 4
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    Hydrogen incorporation in enstatite in the system MgO-SiO2-H2O-NaCl (2018)
    Springer
    Details
    Publication Date: 2021-03-29
    Description: The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na+ on the defect chemistry or an exchange between OH- and Cl-in enstatite, appear much less important. A partition coefficient D Na En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.
    Keywords: KEnstatite; Hydrogen incorporation;Water activity; Sodium; Chlorine ; 551
    Language: English
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  • 5
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    Catshark egg capsules from a Late Eocene deep-water methane-seep deposit in western Washington State, USA (2018)
    Details
    Publication Date: 2021-03-29
    Description: Fossil catshark egg capsules, Scyliorhinotheca goederti gen. et sp. nov., are reported from a Late Eocene deep−water methane−seep calcareous deposit in western Washington State, USA. The capsules are preserved three−dimensionally and some show mineralized remnants of the ribbed capsule wall consisting of small globular crystals that are embedded in a microsparitic matrix. The globules are calcitic, but a strontium content of 2400–3000 ppm suggests that they were origi− nally aragonitic. The carbonate enclosing the egg capsules, and the capsule wall itself, show 13C values as low as −36.5‰, suggesting that formation was induced by the anaerobic oxidation of methane and hence in an anoxic environ− ment. We put forward the following scenario for the mineralization of the capsule wall: (i) the collagenous capsules expe− rienced a sudden change from oxic to anoxic conditions favouring an increase of alkalinity; (ii) this led to the precipitation of aragonitic globules within the collagenous capsule wall; (iii) subsequently the remaining capsule wall was mineralized by calcite or aragonite; (iv) finally the aragonitic parts of the wall recrystallized to calcite. The unusual globular habit of the early carbonate precipitates apparently represents a taphonomic feature, resulting from mineralization mediated by an organic matrix. Taphonomic processes, however, are at best contributed to an increase of alkalinity, which was mostly driven by methane oxidation at the ancient seep site
    Keywords: Elasmobranchia; Scyliorhinidae; taphonomy; exceptional preservation; collagen; Late Eocene; Washing− ton State; USA. ; 551
    Language: English
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  • 6
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    Effects of sample storage and shell orientation on LA-ICPMS trace element measurements on deep-sea mussels. (2018)
    Details
    Publication Date: 2021-03-29
    Description: Geochemical markers are being increasingly applied to fundamental questions in population and community ecology in marine habitats because they allow inferences on individuals dispersal, but vital effects, small sample size and instrumental limitation are still challenging particularly in deep-sea studies. Here we use shells of the deep-sea bivalve Idas modiolaeformis to assess potential effects of sample storage, mineralogy, and valve orientation on LA-ICPMS measurements. Trace element concentrations of (24)Mg, (43)Ca, (88)Sr, (137)Ba, (208)Pb, and (238)U are not affected by the two most commonly used storage methods of biologic deep-sea samples (frozen at -20°C and fixed in 95% ethanol); thus combined analysis of differently preserved specimens is possible when the number of individuals is insufficient and distinct sample fixation is needed for multiple purposes. Valve orientation had a strong impact on quantification of trace elements in the calcitic but not in the aragonitic layer of adult shells. Hence, to enable comparisons between adult shells and entirely aragonitic embryonic shells, a reference map of site-specific signatures can potentially be generated using the aragonitic layer of the adult shells. Understanding ontogenetic changes and environmental effects in trace element incorporation is critical before geochemical fingerprinting can be used as a tool for larval dispersal studies in the deep-sea.
    Keywords: sample storage; shell orientation; LA-ICPMS; deepsea mussels ; 551
    Language: English , English
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  • 7
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    Deciphering fluid inclusions in high-grade rocks (2018)
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    Publication Date: 2021-03-29
    Description: The study of fluid inclusions in high-grade rocks is especially challenging as the host minerals have been normally subjected to deformation, recrystallization and fluid-rock interaction so that primary inclusions, formed at the peak of metamorphism are rare. The larger part of the fluid inclusions found in metamorphic minerals is typically modified during uplift. These late processes may strongly disguise the characteristics of the “original” peak metamorphic fluid. A detailed microstructural analysis of the host minerals, notably quartz, is therefore indispensable for a proper interpretation of fluid inclusions. Cathodoluminescence (CL) techniques combined with trace element analysis of quartz (EPMA, LA-ICPMS) have shown to be very helpful in deciphering the rock-fluid evolution. Whereas high-grade metamorphic quartz may have relatively high contents of trace elements like Ti and Al, low-temperature re-equilibrated quartz typically shows reduced trace element concentrations. The resulting microstructures in CL can be basically distinguished in diffusion patterns (along microfractures and grain boundaries), and secondary quartz formed by dissolution-reprecipitation. Most of these textures are formed during retrograde fluid-controlled processes between ca. 220 and 500 °C, i.e. the range of semi-brittle deformation (greenschist-facies) and can be correlated with the fluid inclusions. In this way modified and re-trapped fluids can be identified, even when there are no optical features observed under the microscope.
    Keywords: Fluid inclusions; Granulite; Charnockite; Cathodoluminescence; LA-ICPMS; Quartz ; 551
    Language: English
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  • 8
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    Protomylonite evolution potentially revealed by the 3D depiction and fractal analysis of chemical data from a feldspar (2018)
    Details
    Publication Date: 2021-03-29
    Description: An alkali feldspar megacryst from a protomylonite has been studied using laser ablation-ICP-mass spectrometry combined with cathodoluminescence imaging, Raman spectroscopy, and electron probe microanalysis. The aim was to determine the original (magmatic) geochemical pattern of the crystal and the changes introduced by protomylonitization. Digital concentration-distribution models, derivative gradient models, and fractal statistics, e.g., Hurst-exponent values are used in a novel way to reveal subtle changes in the trace-element composition of the feldspar. Formation of the crystal is reflected in a slightly chaotic trace-element (Ba, Sr, and Rb) distribution pattern that is more or less characterized by continuous development from a fairly homogeneous environment. Derivative gradient models demonstrate a microdomain pattern. Fractal statistics show that element behavior was changeable, with Ba and Sr always more persistent (continuing) and Rb always less persistent, with the latter showing a tendency to migrate. The variations in the Hurst exponent are, however, too large to be explained by magmatic differentiation alone. The observed element behavior may be explained by structural changes revealed by Raman spectroscopy and CL. In high-strain domains, T–O–T modes become stronger for Si–O–Al than Al–O–Al linkages. Increasing amounts of Al–O−–Al defects are demonstrated by cathodoluminescence. Both may result from small-distance diffusion creep, making the crystal geochemical pattern slightly patchy. In turn, the marginal part of the megacryst has a mosaic of randomly orientated, newly crystallized K-feldspars. The re-growth is confirmed by trace-element distribution patterns and fractal statistics which identify an abrupt change in the transformation environment. The novel set of tools used in this study reveals a complicated history of megacryst formation and transformation that otherwise would be difficult to unravel and decipher.
    Keywords: Alkali feldspar megacryst; Geochemistry; Raman spectroscopy; Fractal statistics; 3D depiction; Protomylonite ; 551
    Language: English
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  • 9
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    Description of an aerodynamic levitation apparatus with applications in Earth sciences (2018)
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    Publication Date: 2021-03-29
    Description: Background: In aerodynamic levitation, solids and liquids are floated in a vertical gas stream. In combination with CO2-laser heating, containerless melting at high temperature of oxides and silicates is possible. We apply aerodynamic levitation to bulk rocks in preparation for microchemical analyses, and for evaporation and reduction experiments. Results: Liquid silicate droplets (~2 mm) were maintained stable in levitation using a nozzle with a 0.8 mm bore and an opening angle of 60°. The gas flow was ~250 ml min-1. Rock powders were melted and homogenized for microchemcial analyses. Laser melting produced chemically homogeneous glass spheres. Only highly (e.g. H2O) and moderately volatile components (Na, K) were partially lost. The composition of evaporated materials was determined by directly combining levitation and inductively coupled plasma mass spectrometry. It is shown that the evaporated material is composed of Na 〉 K 〉〉 Si. Levitation of metal oxide-rich material in a mixture of H2 and Ar resulted in the exsolution of liquid metal. Conclusions: Levitation melting is a rapid technique or for the preparation of bulk rock powders for major, minor and trace element analysis. With exception of moderately volatile elements Na and K, bulk rock analyses can be performed with an uncertainty of ± 5% relative. The technique has great potential for the quantitative determination of evaporated materials from silicate melts. Reduction of oxides to metal is a means for the extraction and analysis of siderophile elements from silicates and can be used to better understand the origin of chondritic metal.
    Keywords: aerodynamic levitation apparatus; Earth sciences ; 551
    Language: English
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  • 10
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    Chemical characteristics (REE, etc.) of Paleozoic and Mesozoic graywackes and sandstones from Central Europe (2018)
    Details
    Publication Date: 2021-03-29
    Description: During the Variscan orogeny in Central Europe, partial melting in the lower continental crust formed granitic magmas, which intruded into the upper crust and left compounds of Ca (plus Eu2+), Mg, etc. in the lower crust. From the late Paleozoic decomposition of the tonalitic upper crust, sedimentary graywackes were produced reflecting the composition of this crust. The repeated reworking of the sedimentary cover caused the formation of sands. Sandstones as their products of consolidation contain increasing fractions of quartz and decreasing feldspar from Carboniferous and Triassic to Cretaceous age. A distinct negative Eu anomaly characterizes the majority of these rocks. The latter is imprinted by the Variscan magmatism. Quartz as used for numerous Medieval wood ash glasses is marked for its Central European origin by a distinct negative Eu anomaly in contrast to many soda glasses produced outside Germany mostly with a small or none Eu anomaly.
    Keywords: Graywackes; Sandstones; Quartz; Rare earth elements; Medieval glass ; 551
    Language: English
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