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  • Blackwell Publishing Ltd  (66,976)
  • American Meteorological Society
  • International Union of Crystallography
  • 2020-2022  (5,103)
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  • 1
    Publication Date: 2021-05-12
    Description: Producing probabilistic subseasonal forecasts of extreme events up to six weeks in advance is crucial for many economic sectors. In agribusiness, this time scale is particularly critical because it allows for mitigation strategies to be adopted for counteracting weather hazards and taking advantage of opportunities. For example, spring frosts are detrimental for many nut trees, resulting in dramatic losses at harvest time. To explore subseasonal forecast quality in boreal spring, identified as one of the most sensitive times of the year by agribusiness end users, we build a multisystem ensemble using four models involved in the Subseasonal to Seasonal Prediction project (S2S). Two-meter temperature forecasts are used to analyze cold spell predictions in the coastal Black Sea region, an area that is a global leader in the production of hazelnuts. When analyzed at the global scale, the multisystem ensemble probabilistic forecasts for near-surface temperature are better than climatological values for several regions, especially the tropics, even many weeks in advance; however, in the coastal Black Sea, skill is low after the second forecast week. When cold spells are predicted instead of near-surface temperatures, skill improves for the region, and the forecasts prove to contain potentially useful information to stakeholders willing to put mitigation plans into effect. Using a cost–loss model approach for the first time in this context, we show that there is added value of having such a forecast system instead of a business-as-usual strategy, not only for predictions released 1–2 weeks ahead of the extreme event, but also at longer lead times.
    Description: Published
    Description: 237–254
    Description: 4A. Oceanografia e clima
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2020-07-13
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 3
    Publication Date: 2021-06-28
    Description: Efforts to collaboratively manage the risk of flooding are ultimately based on individuals learning about risks, the decision process, and the effectiveness of decisions made in prior situations. This article argues that much can be learned about a governance setting by explicitly evaluating the relationships through which influential individuals and their immediate contacts receive and send information to one another. We define these individuals as “brokers,” and the networks that emerge from their interactions as “learning spaces.” The aim of this article is to develop strategies to identify and evaluate the properties of a broker's learning space that are indicative of a collaborative flood risk management arrangement. The first part of this article introduces a set of indicators, and presents strategies to employ this list so as to systematically identify brokers, and compare their learning spaces. The second part outlines the lessons from an evaluation that explored cases in two distinct flood risk management settings in Germany. The results show differences in the observed brokers' learning spaces. The contacts and interactions of the broker in Baden‐Württemberg imply a collaborative setting. In contrast, learning space of the broker in North Rhine‐Westphalia lacks the same level of diversity and polycentricity.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: MWK Baden‐Württemberg
    Keywords: 333.91 ; brokerage ; collaborative water governance ; comanagement ; comparative analysis ; social networks
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  • 4
    Publication Date: 2021-03-30
    Description: In the past two decades, most of the steps in a macromolecular crystallography experiment have undergone tremendous development with respect to speed, feasibility and increase of throughput. The part of the experimental workflow that is still a bottleneck, despite significant efforts, involves the manipulation and harvesting of the crystals for the diffraction experiment. Here, a novel low‐cost device is presented that functions as a cover for 96‐well crystallization plates. This device enables access to the individual experiments one at a time by its movable parts, while minimizing evaporation of all other experiments of the plate. In initial tests, drops of many typically used crystallization cocktails could be successfully protected for up to 6 h. Therefore, the manipulation and harvesting of crystals is straightforward for the experimenter, enabling significantly higher throughput. This is useful for many macromolecular crystallography experiments, especially multi‐crystal screening campaigns.
    Description: A simple and low‐cost device has been developed to minimize evaporation in microtiter plates for easy crystal handling and harvesting. image
    Keywords: 548 ; evaporation reduction ; crystal handling ; crystal harvesting ; crystallographic fragment screening
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  • 5
    Publication Date: 2021-03-30
    Description: Multiple‐Edge Anomalous Diffraction (MEAD) has been applied to various quaternary sulfosalts belonging to the adamantine compound family in order to validate the distribution of copper, zinc and iron cations in the structure. Semiconductors from this group of materials are promising candidates for photovoltaic applications. Their properties strongly depend on point defects, in particular related to cation order–disorder. However, Cu+, Zn2+ and Fe2+ have very similar scattering factors and are all but indistinguishable in usual X‐ray diffraction experiments. Anomalous diffraction utilizes the dependency of the atomic scattering factors f′ and f′′ of the energy of the radiation, especially close to the element‐specific absorption edges. In the MEAD technique, individual Bragg peaks are tracked over an absorption edge. The intensity changes depending on the structure factor can be highly characteristic for Miller indices selected for a specific structural problem, but require very exact measurements. Beamline KMC‐2 at synchrotron BESSY II, Berlin, has been recently upgraded for this technique. Anomalous X‐ray powder diffraction and XAFS compliment the data. Application of this technique confirmed established cation distribution in Cu2ZnSnSe4 (CZTSe) and Cu2FeSnS4 (CFTS). In contrast to the literature, cation distribution in Cu2ZnSiSe4 (CZSiSe) is shown to adopt a highly ordered wurtz‐kesterite structure type.
    Description: Multiple‐Edge Anomalous Diffraction (MEAD) has been applied to various quaternary sulfosalts belonging to the adamantine compound family in order to validate the distribution of copper, zinc and iron cations in the structure. Application of this technique confirms established cation distribution in Cu2ZnSnSe4 (CZTSe) and Cu2FeSnS4 (CFTS), but in Cu2ZnSiSe4 (CZSiSe) the cation distribution is shown to adopt a highly ordered wurtz‐kesterite structure type in contrast to the literature. image
    Keywords: 548 ; synchrotron ; anomalous diffraction ; semiconductor ; MEAD
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  • 6
    Publication Date: 2021-03-27
    Description: The growth of diffraction‐quality crystals and experimental phasing remain two of the main bottlenecks in protein crystallography. Here, the high‐affinity copper(II)‐binding tripeptide GHK was fused to the N‐terminus of a GFP variant and an MBP‐FG peptide fusion. The GHK tag promoted crystallization, with various residues (His, Asp, His/Pro) from symmetry molecules completing the copper(II) square‐pyramidal coordination sphere. Rapid structure determination by copper SAD phasing could be achieved, even at a very low Bijvoet ratio or after significant radiation damage. When collecting highly redundant data at a wavelength close to the copper absorption edge, residual S‐atom positions could also be located in log‐likelihood‐gradient maps and used to improve the phases. The GHK copper SAD method provides a convenient way of both crystallizing and phasing macromolecular structures, and will complement the current trend towards native sulfur SAD and MR‐SAD phasing.
    Description: A novel three‐residue tag containing the residues GHK that can be used to promote crystallization and in SAD phasing experiments using its tightly bound copper ion is described. image
    Keywords: 548 ; phasing ; crystallization ; GHK ; SAD
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  • 7
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    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-03-30
    Description: Recently, the authors reported on the development of crystallinity in mixed‐tacticity polyhydroxybutyrates. Comparable values reported in the literature vary depending on the manner of determination, the discrepancies being partially attributable to scattering from paracrystalline portions of the material. These portions can be qualified by peak profile fitting or quantified by allocation of scattered X‐ray intensities. However, the latter requires a good quality of the former, which in turn must additionally account for peak broadening inherent in the measurement setup, and due to limited crystallite sizes and the possible presence of microstrain. Since broadening due to microstrain and paracrystalline order both scale with scattering vector, they are easily confounded. In this work, a method to directionally discern these two influences on the peak shape in a Rietveld refinement is presented. Allocating intensities to amorphous, bulk and paracrystalline portions with changing tactic disturbance provided internal validations of the obtained directional numbers. In addition, the correlation between obtained thermal factors and Young's moduli, determined in earlier work, is discussed.
    Description: A method to robustly determine paracrystalline contents from Rietveld‐refined powder X‐ray data is presented and discussed for the example of mixed‐tacticity polyhydroxybutyrates. image
    Keywords: 548 ; polyhydroxybutyrates ; mixed tacticity ; paracrystallinity ; Rietveld refinement ; thermal factors
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  • 8
    Publication Date: 2021-03-27
    Description: Two evaluation concepts for nondestructive depth‐resolved X‐ray residual stress analysis in the near‐surface region of materials with cubic symmetry and nearly single crystalline structure are introduced by simulated examples. Both concepts are based on the same data acquisition strategy, which consists in the determination of lattice‐spacing depth profiles along the ⟨hkl⟩ poles by stepwise sample rotation around the scattering vector. Segmentation of these profiles parallel to the sample surface provides the lattice strain state as a function of depth. The first evaluation concept extends the crystallite group method developed for materials with pronounced crystallographic texture by the feature of depth resolution and can be applied to samples with arbitrary orientation. The second evaluation concept, which adapts the linear regression approach of the sin2ψ method for the case of single crystalline materials, is restricted to samples with (001) orientation. The influence of the strain‐free lattice parameter a0 on residual stress analysis using both evaluation concepts is discussed on the basis of explicitly derived relations.
    Description: Two data evaluation concepts are proposed for nondestructive and depth‐resolved X‐ray residual stress analysis by means of energy‐dispersive diffraction on materials featuring cubic symmetry and a nearly single crystalline structure. image
    Keywords: 548 ; residual stress ; X‐ray diffraction ; depth‐resolved analysis ; mosaic crystals
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  • 9
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    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-03-30
    Description: Dichroism is one of the most important optical effects in both the visible and the X‐ray range. Besides absorption, scattering can also contribute to dichroism. This paper demonstrates that, based on the example of polyimide, materials can show tiny dichroism even far from electronic resonances due to scattering. Although the effect is small, it can lead to a measurable polarization change and might have influence on highly sensitive polarimetric experiments.
    Description: Aligned molecules, for example in polyimide foils, lead to small dichroism even far from resonances, which can be revealed by high‐precision X‐ray polarimetry. image
    Keywords: 548 ; polyimide ; polarization ; X‐ray polarimetry ; wide‐angle scattering ; X‐ray dichroism
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  • 10
    Publication Date: 2021-03-27
    Description: The complete elastic stiffness tensor of thiourea has been determined from thermal diffuse scattering (TDS) using high‐energy photons (100 keV). Comparison with earlier data confirms a very good agreement of the tensor coefficients. In contrast with established methods to obtain elastic stiffness coefficients (e.g. Brillouin spectroscopy, inelastic X‐ray or neutron scattering, ultrasound spectroscopy), their determination from TDS is faster, does not require large samples or intricate sample preparation, and is applicable to opaque crystals. Using high‐energy photons extends the applicability of the TDS‐based approach to organic compounds which would suffer from radiation damage at lower photon energies.
    Description: The elastic stiffness coefficients of thiourea are determined from thermal diffuse scattering. image
    Keywords: 548 ; thermal diffuse scattering ; elastic stiffness ; thiourea
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  • 11
    Publication Date: 2021-07-03
    Description: X‐ray reflectivity (XRR) is a powerful and popular scattering technique that can give valuable insight into the growth behavior of thin films. This study shows how a simple artificial neural network model can be used to determine the thickness, roughness and density of thin films of different organic semiconductors [diindenoperylene, copper(II) phthalocyanine and α‐sexithiophene] on silica from their XRR data with millisecond computation time and with minimal user input or a priori knowledge. For a large experimental data set of 372 XRR curves, it is shown that a simple fully connected model can provide good results with a mean absolute percentage error of 8–18% when compared with the results obtained by a genetic least mean squares fit using the classical Parratt formalism. Furthermore, current drawbacks and prospects for improvement are discussed.
    Description: Artificial neural networks trained with simulated data are shown to correctly and quickly determine film parameters from experimental X‐ray reflectivity curves.
    Keywords: 548 ; X‐ray reflectivity ; machine learning ; organic semi‐conductors ; neural networks
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  • 12
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    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-05
    Description: Coordinate‐free expressions for the form factors of arbitrary polygons and polyhedra are derived using the divergence theorem and Stokes's theorem. Apparent singularities, all removable, are discussed in detail. Cancellation near the singularities causes a loss of precision that can be avoided by using series expansions. An important application domain is small‐angle scattering by nanocrystals.
    Description: Coordinate‐free expressions for the form factors of arbitrary polygons and polyhedra are derived using the divergence theorem and Stokes's theorem. Series expansions are used to ensure numeric precision close to apparent singularities. image
    Keywords: 548 ; form factors ; polyhedra ; Fourier shape transform
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  • 13
    Publication Date: 2021-06-30
    Description: ROBL‐II provides four different experimental stations to investigate actinide and other alpha‐ and beta‐emitting radionuclides at the new EBS storage ring of ESRF within an energy range of 3 to 35 keV. The XAFS station consists of a highly automatized, high sample throughput installation in a glovebox, to measure EXAFS and conventional XANES of samples routinely at temperatures down to 10 K, and with a detection limit in the sub‐p.p.m. range. The XES station with its five bent‐crystal analyzer, Johann‐type setup with Rowland circles of 1.0 and 0.5 m radii provides high‐energy resolution fluorescence detection (HERFD) for XANES, XES, and RIXS measurements, covering both actinide L and M edges together with other elements accessible in the 3 to 20 keV energy range. The six‐circle heavy duty goniometer of XRD‐1 is equipped for both high‐resolution powder diffraction as well as surface‐sensitive CTR and RAXR techniques. Single crystal diffraction, powder diffraction with high temporal resolution, as well as X‐ray tomography experiments can be performed at a Pilatus 2M detector stage (XRD‐2). Elaborate radioprotection features enable a safe and easy exchange of samples between the four different stations to allow the combination of several methods for an unprecedented level of information on radioactive samples for both fundamental and applied actinide and environmental research.
    Description: ROBL‐II at ESRF provides four experimental stations to investigate actinides with X‐ray absorption and emission spectroscopy, and with surface, high‐resolution powder, and single‐crystal X‐ray diffractometry.
    Keywords: 549 ; actinides ; EXAFS ; XANES ; HERFD‐XANES ; XAS ; XES ; RIXS ; XRD ; CTR ; RAXR ; surface diffraction
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  • 14
    Publication Date: 2021-03-30
    Description: The ATSAS software suite encompasses a number of programs for the processing, visualization, analysis and modelling of small‐angle scattering data, with a focus on the data measured from biological macromolecules. Here, new developments in the ATSAS 3.0 package are described. They include IMSIM, for simulating isotropic 2D scattering patterns; IMOP, to perform operations on 2D images and masks; DATRESAMPLE, a method for variance estimation of structural invariants through parametric resampling; DATFT, which computes the pair distance distribution function by a direct Fourier transform of the scattering data; PDDFFIT, to compute the scattering data from a pair distance distribution function, allowing comparison with the experimental data; a new module in DATMW for Bayesian consensus‐based concentration‐independent molecular weight estimation; DATMIF, an ab initio shape analysis method that optimizes the search model directly against the scattering data; DAMEMB, an application to set up the initial search volume for multiphase modelling of membrane proteins; ELLLIP, to perform quasi‐atomistic modelling of liposomes with elliptical shapes; NMATOR, which models conformational changes in nucleic acid structures through normal mode analysis in torsion angle space; DAMMIX, which reconstructs the shape of an unknown intermediate in an evolving system; and LIPMIX and BILMIX, for modelling multilamellar and asymmetric lipid vesicles, respectively. In addition, technical updates were deployed to facilitate maintainability of the package, which include porting the PRIMUS graphical interface to Qt5, updating SASpy – a PyMOL plugin to run a subset of ATSAS tools – to be both Python 2 and 3 compatible, and adding utilities to facilitate mmCIF compatibility in future ATSAS releases. All these features are implemented in ATSAS 3.0, freely available for academic users at https://www.embl‐hamburg.de/biosaxs/software.html.
    Description: ATSAS is a comprehensive software suite for the processing, visualization, analysis and modelling of small‐angle scattering data. This article describes developments in the ATSAS 3.0 release, including new programs for data simulation and for the structural modelling of lipids, nucleic acids and polydisperse systems. image
    Keywords: 548 ; small‐angle scattering ; data analysis ; biological macromolecules ; structural modelling ; ATSAS
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  • 15
    Publication Date: 2021-07-04
    Description: Most common machine learning (ML) algorithms usually work well on balanced training sets, that is, datasets in which all classes are approximately represented equally. Otherwise, the accuracy estimates may be unreliable and classes with only a few values are often misclassified or neglected. This is known as a class imbalance problem in machine learning and datasets that do not meet this criterion are referred to as imbalanced data. Most datasets of soil classes are, therefore, imbalanced data. One of our main objectives is to compare eight resampling strategies that have been developed to counteract the imbalanced data problem. We compared the performance of five of the most common ML algorithms with the resampling approaches. The highest increase in prediction accuracy was achieved with SMOTE (the synthetic minority oversampling technique). In comparison to the baseline prediction on the original dataset, we achieved an increase of about 10, 20 and 10% in the overall accuracy, kappa index and F‐score, respectively. Regarding the ML approaches, random forest (RF) showed the best performance with an overall accuracy, kappa index and F‐score of 66, 60 and 57%, respectively. Moreover, the combination of RF and SMOTE improved the accuracy of the individual soil classes, compared to RF trained on the original dataset and allowed better prediction of soil classes with a low number of samples in the corresponding soil profile database, in our case for Chernozems. Our results show that balancing existing soil legacy data using synthetic sampling strategies can significantly improve the prediction accuracy in digital soil mapping (DSM). Highlights Spatial distribution of soil classes in Iran can be predicted using machine learning (ML) algorithms. The synthetic minority oversampling technique overcomes the drawback of imbalanced and highly biased soil legacy data. When combining a random forest model with synthetic sampling strategies the prediction accuracy of the soil model improves significantly. The resulting new soil map of Iran has a much higher spatial resolution compared to existing maps and displays new soil classes that have not yet been mapped in Iran.
    Description: Alexander von Humboldt‐Stiftung http://dx.doi.org/10.13039/100005156
    Description: German Research Foundation http://dx.doi.org/10.13039/501100001659
    Description: Soil and Water Research Institute, Agricultural Research, Education and Extension Organization, Karaj, Iran
    Keywords: 631.4 ; covariates ; imbalanced data ; machine learning ; random forest ; soil legacy data
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  • 16
    Publication Date: 2021-03-27
    Description: Serial crystallography records still diffraction patterns from single, randomly oriented crystals, then merges data from hundreds or thousands of them to form a complete data set. To process the data, the diffraction patterns must first be indexed, equivalent to determining the orientation of each crystal. A novel automatic indexing algorithm is presented, which in tests usually gives significantly higher indexing rates than alternative programs currently available for this task. The algorithm does not require prior knowledge of the lattice parameters but can make use of that information if provided, and also allows indexing of diffraction patterns generated by several crystals in the beam. Cases with a small number of Bragg spots per pattern appear to particularly benefit from the new approach. The algorithm has been implemented and optimized for fast execution, making it suitable for real‐time feedback during serial crystallography experiments. It is implemented in an open‐source C++ library and distributed under the LGPLv3 licence. An interface to it has been added to the CrystFEL software suite.
    Description: A description and evaluation are given of XGANDALF, extended gradient descent algorithm for lattice finding, an algorithm developed for fast and accurate indexing of snapshot diffraction patterns. image
    Keywords: 548 ; indexing ; XGANDALF ; CrystFEL ; multiple lattices ; serial crystallography
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  • 17
    Publication Date: 2021-03-27
    Description: A crystallographic indexing algorithm, pinkIndexer, is presented for the analysis of snapshot diffraction patterns. It can be used in a variety of contexts including measurements made with a monochromatic radiation source, a polychromatic source or with radiation of very short wavelength. As such, the algorithm is particularly suited to automated data processing for two emerging measurement techniques for macromolecular structure determination: serial pink‐beam X‐ray crystallography and serial electron crystallography, which until now lacked reliable programs for analyzing many individual diffraction patterns from crystals of uncorrelated orientation. The algorithm requires approximate knowledge of the unit‐cell parameters of the crystal, but not the wavelengths associated with each Bragg spot. The use of pinkIndexer is demonstrated by obtaining 1005 lattices from a published pink‐beam serial crystallography data set that had previously yielded 140 indexed lattices. Additionally, in tests on experimental serial crystallography diffraction data recorded with quasi‐monochromatic X‐rays and with electrons the algorithm indexed more patterns than other programs tested.
    Description: pinkIndexer, an algorithm developed for indexing of snapshot diffraction patterns recorded with pink‐beam X‐rays, monochromatic X‐rays and electrons, is described and its use evaluated. image
    Keywords: 548 ; indexing ; pinkIndexer ; CrystFEL ; pink X‐ray beam ; serial electron diffraction
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  • 18
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    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-17
    Description: CRM1 is a nuclear export receptor that has been intensively targeted over the last decade for the development of antitumor and antiviral drugs. Structural analysis of several inhibitor compounds bound to CRM1 revealed that their mechanism of action relies on the covalent modification of a critical cysteine residue (Cys528 in the human receptor) located in the nuclear export signal‐binding cleft. This study presents the crystal structure of human CRM1, covalently modified by 2‐mercaptoethanol on Cys528, in complex with RanGTP at 2.58 Å resolution. The results demonstrate that buffer components can interfere with the characterization of cysteine‐dependent inhibitor compounds.
    Description: The covalent modification of human CRM1 by 2‐mercaptoethanol interferes with the characterization of cysteine‐dependent inhibitor compounds. image
    Keywords: 548 ; nuclear export ; cancer ; exportin 1 ; cysteine modification
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  • 19
    Publication Date: 2021-06-16
    Description: The application of biochar to agricultural soils to increase nutrient availability, crop production and carbon sequestration has gained increasing interest but data from field experiments on temperate, marginal soils are still under‐represented. In the current study, biochar, produced from organic residues (digestates) from a biogas plant, was applied with and without digestates at low (3.4 t ha−1) and intermediate (17.1 t ha−1) rates to two acidic and sandy soils in northern Germany that are used for corn (Zea mays L.) production. Soil nutrient availability, crop yields, microbial biomass and carbon dioxide (CO2) emissions from heterotrophic respiration were measured over two consecutive years. The effects of biochar application depended on the intrinsic properties of the two tested soils and the biochar application rates. Although the soils at the fallow site, with initially low nutrient concentrations, showed a significant increase in pH, soil nutrients and crop yield after low biochar application rates, a similar response was found at the cornfield site only after application of substantially larger amounts of biochar. The effect of a single dose of biochar at the beginning of the experiment diminished over time but was still detectable after 2 years. Whereas plant available nutrient concentrations increased after biochar application, the availability of potentially phytotoxic trace elements (Zn, Pb, Cd, Cr) decreased significantly, and although slight increases in microbial biomass carbon and heterotrophic CO2 fluxes were observed after biochar application, they were mostly not significant. The results indicate that the application of relatively small amounts of biochar could have positive effects on plant available nutrients and crop yields of marginal arable soils and may decrease the need for mineral fertilizers while simultaneously increasing the sequestration of soil organic carbon. Highlights A low rate of biochar increased plant available nutrients and crop yield on marginal soils. Biochar application reduced the availability of potentially harmful trace elements. Heterotrophic respiration showed no clear response to biochar application. Biochar application may reduce fertilizer need and increase carbon sequestration on marginal soils.
    Description: German Academic Exchange Service http://dx.doi.org/10.13039/501100001655
    Description: Institute Strategic Programme grants, “Soils to Nutrition”
    Keywords: 631.4 ; black carbon ; carbon sequestration ; corn ; digestate ; heterotrophic respiration ; marginal soils ; microbial biomass
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  • 20
    Publication Date: 2021-06-26
    Description: Owing to the development of X‐ray focusing optics during the past decades, synchrotron‐based X‐ray microscopy techniques allow the study of specimens with unprecedented spatial resolution, down to 10 nm, using soft and medium X‐ray photon energies, though at the expense of the field of view (FOV). One of the approaches to increase the FOV to square millimetres is raster‐scanning of the specimen using a single nanoprobe; however, this results in a long data acquisition time. This work employs an array of inclined biconcave parabolic refractive multi‐lenses (RMLs), fabricated by deep X‐ray lithography and electroplating to generate a large number of long X‐ray foci. Since the FOV is limited by the pattern height if a single RML is used by impinging X‐rays parallel to the substrate, many RMLs at regular intervals in the orthogonal direction were fabricated by tilted exposure. By inclining the substrate correspondingly to the tilted exposure, 378000 X‐ray line foci were generated with a length in the centimetre range and constant intervals in the sub‐micrometre range. The capability of this new X‐ray focusing device was first confirmed using ray‐tracing simulations and then using synchrotron radiation at BL20B2 of SPring‐8, Japan. Taking account of the fact that the refractive lens is effective for focusing high‐energy X‐rays, the experiment was performed with 35 keV X‐rays. Next, by scanning a specimen through the line foci, this device was used to perform large FOV pixel super‐resolution scanning transmission hard X‐ray microscopy (PSR‐STHXM) with a 780 ± 40 nm spatial resolution within an FOV of 1.64 cm × 1.64 cm (limited by the detector area) and a total scanning time of 4 min. Biomedical implant abutments fabricated via selective laser melting using Ti–6Al–4V medical alloy were measured by PSR‐STHXM, suggesting its unique potential for studying extended and thick specimens. Although the super‐resolution function was realized in one dimension in this study, it can be expanded to two dimensions by aligning a pair of presented devices orthogonally.
    Description: A new X‐ray focusing device generates hundreds of thousands of line foci, periodically spaced in the sub‐micrometre range, with centimetre length. It enables to achieve large FOV pixel super‐resolution scanning transmission hard X‐ray microscopy. image
    Keywords: 502.82 ; inclined refractive X‐ray multi‐lens array ; pixel super‐resolution ; scanning transmission hard X‐ray microscopy ; deep X‐ray lithography and electroplating
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  • 21
    Publication Date: 2021-07-02
    Description: A new concept for temporal gating of synchrotron X‐ray pulses based on laser‐induced thermal transient gratings is presented. First experimental tests of the concept yield a diffraction efficiency of 0.18%; however, the calculations indicate a theoretical efficiency and contrast of 〉30% and 10−5, respectively. The full efficiency of the pulse picker has not been reached yet due to a long‐range thermal deformation of the sample after absorption of the excitation laser. This method can be implemented in a broad spectral range (100 eV to 20 keV) and is only minimally invasive to an existing setup.
    Description: A new concept for temporal gating of synchrotron X‐ray pulses based on laser‐induced thermal transient gratings is presented.
    Keywords: 548 ; synchrotron ; time‐resolved ; thermal deformation ; transient grating ; pulse picking
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  • 22
    Publication Date: 2021-06-06
    Description: The time‐resolved hard X‐ray diffraction endstation KMC‐3 XPP for optical pump/X‐ray probe experiments at the electron storage ring BESSY II is dedicated to investigating the structural response of thin film samples and heterostructures after their excitation with ultrashort laser pulses and/or electric field pulses. It enables experiments with access to symmetric and asymmetric Bragg reflections via a four‐circle diffractometer and it is possible to keep the sample in high vacuum and vary the sample temperature between ∼15 K and 350 K. The femtosecond laser system permanently installed at the beamline allows for optical excitation of the sample at 1028 nm. A non‐linear optical setup enables the sample excitation also at 514 nm and 343 nm. A time‐resolution of 17 ps is achieved with the `low‐α' operation mode of the storage ring and an electronic variation of the delay between optical pump and hard X‐ray probe pulse conveniently accesses picosecond to microsecond timescales. Direct time‐resolved detection of the diffracted hard X‐ray synchrotron pulses use a gated area pixel detector or a fast point detector in single photon counting mode. The range of experiments that are reliably conducted at the endstation and that detect structural dynamics of samples excited by laser pulses or electric fields are presented.
    Description: The KMC‐3 XPP endstation of the synchrotron BESSY II is dedicated to time‐resolved studies of structural dynamics of matter upon optical and/or electrical excitation using hard X‐ray diffraction with an accessible time range from 17 ps to several microseconds. image
    Keywords: 548 ; beamline instrumentation ; time‐resolved X‐ray diffraction ; optical excitation ; thermal transport ; ferroelectric switching
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  • 23
    Publication Date: 2021-06-27
    Description: Social inequalities lead to flood resilience inequalities across social groups, a topic that requires improved documentation and understanding. The objective of this paper is to attend to these differences by investigating self‐stated flood recovery across genders in Vietnam as a conceptual replication of earlier results from Germany. This study employs a regression‐based analysis of 1,010 respondents divided between a rural coastal and an urban community in Thua Thien‐Hue province. The results highlight an important set of recovery process‐related variables. The set of relevant variables is similar across genders in terms of inclusion and influence, and includes age, social capital, internal and external support after a flood, perceived severity of previous flood impacts, and the perception of stress‐resilience. However, women were affected more heavily by flooding in terms of longer recovery times, which should be accounted for in risk management. Overall, the studied variables perform similarly in Vietnam and Germany. This study, therefore, conceptually replicates previous results suggesting that women display slightly slower recovery levels as well as that psychological variables influence recovery rates more than adverse flood impacts. This provides an indication of the results' potentially robust nature due to the different socio‐environmental contexts in Germany and Vietnam.
    Keywords: 333.7 ; flood recovery ; resilience ; societal equity ; vulnerability
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  • 24
    Publication Date: 2021-03-27
    Description: The crystal structures of sodium ethoxide (sodium ethanolate, NaOEt), sodium n‐propoxide (sodium n‐propanolate, NaOnPr), sodium n‐butoxide (sodium n‐butanolate, NaOnBu) and sodium n‐pentoxide (sodium n‐amylate, NaOnAm) were determined from powder X‐ray diffraction data. NaOEt crystallizes in space group P421m, with Z = 2, and the other alkoxides crystallize in P4/nmm, with Z = 2. To resolve space‐group ambiguities, a Bärnighausen tree was set up, and Rietveld refinements were performed with different models. In all structures, the Na and O atoms form a quadratic net, with the alkyl groups pointing outwards on both sides (anti‐PbO type). The alkyl groups are disordered. The disorder becomes even more pronounced with increasing chain length. Recrystallization from the corresponding alcohols yielded four sodium alkoxide solvates: sodium ethoxide ethanol disolvate (NaOEt·2EtOH), sodium n‐propoxide n‐propanol disolvate (NaOnPr·2nPrOH), sodium isopropoxide isopropanol pentasolvate (NaOiPr·5iPrOH) and sodium tert‐amylate tert‐amyl alcohol monosolvate (NaOtAm·tAmOH, tAm = 2‐methyl‐2‐butyl). Their crystal structures were determined by single‐crystal X‐ray diffraction. All these solvates form chain structures consisting of Na+, –O− and –OH groups, encased by alkyl groups. The hydrogen‐bond networks diverge widely among the solvate structures. The hydrogen‐bond topology of the iPrOH network in NaOiPr·5iPrOH shows branched hydrogen bonds and differs considerably from the networks in pure crystalline iPrOH.
    Description: The crystal structures of NaOEt, NaOPr, NaOBu and NaOAm (Am = amyl = pentyl) were determined from powder data. These compounds crystallize in an anti‐PbO structure in the space groups P21m and P4/nmm. Additionally, solvates with the composition NaOEt·2EtOH, NaOPr·2PrOH, NaOiPr·5iPrOH and NaOtAm·tAmOH were synthesized, and their structures were determined from single crystals. They form interesting chain structures of different compositions and topologies. image
    Keywords: 548 ; sodium alkoxide ; powder data ; solvate ; isopropanol ; Bärnighausen tree ; PXRD
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  • 25
    Publication Date: 2021-07-05
    Description: Nitrogen (N) fertilization is the major contributor to nitrous oxide (N2O) emissions from agricultural soil, especially in post‐harvest seasons. This study was carried out to investigate whether ryegrass serving as cover crop affects soil N2O emissions and denitrifier community size. A microcosm experiment was conducted with soil planted with perennial ryegrass (Lolium perenne L.) and bare soil, each with four levels of N fertilizer (0, 5, 10 and 20 g N m−2; applied as calcium ammonium nitrate). The closed‐chamber approach was used to measure soil N2O fluxes. Real‐time PCR was used to estimate the biomass of bacteria and fungi and the abundance of genes involved in denitrification in soil. The results showed that the presence of ryegrass decreased the nitrate content in soil. Cumulative N2O emissions of soil with grass were lower than in bare soil at 5 and 10 g N m−2. Fertilization levels did not affect the abundance of soil bacteria and fungi. Soil with grass showed greater abundances of bacteria and fungi, as well as microorganisms carrying narG, napA, nirK, nirS and nosZ clade I genes. It is concluded that ryegrass serving as a cover crop holds the potential to mitigate soil N2O emissions in soils with moderate or high NO3− concentrations. This highlights the importance of cover crops for the reduction of N2O emissions from soil, particularly following N fertilization. Future research should explore the full potential of ryegrass to reduce soil N2O emissions under field conditions as well as in different soils. Highlights This study was to investigate whether ryegrass serving as cover crop affects soil N2O emissions and denitrifier community size; Plant reduced soil N substrates on one side, but their root exudates stimulated denitrification on the other side; N2O emissions were lower in soil with grass than bare soil at medium fertilizer levels, and growing grass stimulated the proliferation of almost all the denitrifying bacteria except nosZ clade II; Ryegrass serving as a cover crop holds the potential to mitigate soil N2O emissions.
    Description: China Scholarship Council http://dx.doi.org/10.13039/501100004543
    Description: The National Science Project for University of Anhui Province
    Keywords: 551.9 ; 631.4 ; denitrification ; perennial ryegrass (Lolium perenne L.) ; soil bacteria ; soil CO2 emissions ; soil N2O emissions
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  • 26
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-03-27
    Description: Small‐angle X‐ray scattering from GaN nanowires grown on Si(111) is measured in the grazing‐incidence geometry and modelled by means of a Monte Carlo simulation that takes into account the orientational distribution of the faceted nanowires and the roughness of their side facets. It is found that the scattering intensity at large wavevectors does not follow Porod's law I(q) ∝ q−4. The intensity depends on the orientation of the side facets with respect to the incident X‐ray beam. It is maximum when the scattering vector is directed along a facet normal, reminiscent of surface truncation rod scattering. At large wavevectors q, the scattering intensity is reduced by surface roughness. A root‐mean‐square roughness of 0.9 nm, which is the height of just 3–4 atomic steps per micrometre‐long facet, already gives rise to a strong intensity reduction.
    Description: The intensity of small‐angle X‐ray scattering from GaN nanowires on Si(111) depends on the orientation of the side facets with respect to the incident beam. This reminiscence of truncation rod scattering gives rise to a deviation from Porod's law. A roughness of just 3–4 atomic steps per micrometre‐long side facet notably changes the intensity curves. image
    Keywords: 548 ; nanowires ; Porod's law ; facet truncation rods ; small‐angle X‐ray scattering ; SAXS ; grazing‐incidence small‐angle X‐ray scattering ; GISAXS
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  • 27
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-28
    Description: Recent developments in cryogenic electron microscopy (cryo‐EM) have enabled structural studies of large macromolecular complexes at resolutions previously only attainable using macromolecular crystallography. Although a number of methods can already assist in de novo building of models into high‐resolution cryo‐EM maps, automated and reliable map interpretation remains a challenge. Presented here is a systematic study of the accuracy of models built into cryo‐EM maps using ARP/wARP. It is demonstrated that the local resolution is a good indicator of map interpretability, and for the majority of the test cases ARP/wARP correctly builds 90% of main‐chain fragments in regions where the local resolution is 4.0 Å or better. It is also demonstrated that the coordinate accuracy for models built into cryo‐EM maps is comparable to that of X‐ray crystallographic models at similar local cryo‐EM and crystallographic resolutions. The model accuracy also correlates with the refined atomic displacement parameters.
    Keywords: 548 ; ARP/wARP ; model building ; cryo‐EM ; model accuracy ; sequence assignment
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  • 28
    Publication Date: 2021-06-05
    Description: Carbonates containing CO4 groups as building blocks have recently been discovered. A new orthocarbonate, Sr2CO4 is synthesized at 92 GPa and at a temperature of 2500 K. Its crystal structure was determined by in situ synchrotron single‐crystal X‐ray diffraction, selecting a grain from a polycrystalline sample. Strontium orthocarbonate crystallizes in the orthorhombic crystal system (space group Pnma) with CO4, SrO9 and SrO11 polyhedra as the main building blocks. It is isostructural to Ca2CO4. DFT calculations reproduce the experimental findings very well and have, therefore, been used to predict the equation of state, Raman and IR spectra, and to assist in the discussion of bonding in this compound.
    Description: A new orthocarbonate, Sr2CO4, was synthesized under extreme pressure and temperature conditions of 92 GPa and 2500 K, respectively. The crystal structure of the compound s fully characterized in situ by synchrotron single‐crystal X‐ray diffraction and DFT calculations were employed to provide insight into its equation of state, Raman and IR spectra, and bonding. image
    Keywords: 548 ; orthocarbonates ; crystal structure ; single‐crystal X‐ray diffraction ; high pressure ; Sr2CO4
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  • 29
    Publication Date: 2021-06-28
    Description: Small‐angle X‐ray scattering (SAXS) is an established method for studying nanostructured systems and in particular biological macromolecules in solution. To obtain element‐specific information about the sample, anomalous SAXS (ASAXS) exploits changes of the scattering properties of selected atoms when the energy of the incident X‐rays is close to the binding energy of their electrons. While ASAXS is widely applied to condensed matter and inorganic systems, its use for biological macromolecules is challenging because of the weak anomalous effect. Biological objects are often only available in small quantities and are prone to radiation damage, which makes biological ASAXS measurements very challenging. The BioSAXS beamline P12 operated by the European Molecular Biology Laboratory (EMBL) at the PETRA III storage ring (DESY, Hamburg) is dedicated to studies of weakly scattering objects. Here, recent developments at P12 allowing for ASAXS measurements are presented. The beamline control, data acquisition and data reduction pipeline of the beamline were adapted to conduct ASAXS experiments. Modelling tools were developed to compute ASAXS patterns from atomic models, which can be used to analyze the data and to help designing appropriate data collection strategies. These developments are illustrated with ASAXS experiments on different model systems performed at the P12 beamline.
    Keywords: 548 ; ASAXS ; biological SAXS ; metalloproteins ; gold nanoparticles ; anomalous scattering ; beamline development
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  • 30
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-27
    Description: Binary III–V nitrides such as AlN, GaN and InN in the wurtzite‐type structure have long been considered as potent semiconducting materials because of their optoelectronic properties, amongst others. With rising concerns over the utilization of scarce elements, a replacement of the trivalent cations by others in ternary and multinary nitrides has led to the development of different variants of nitrides and oxide nitrides crystallizing in lower‐symmetry variants of wurtzite. This work presents the symmetry relationships between these structural types specific to nitrides and oxide nitrides and updates some prior work on this matter. The non‐existence of compounds crystallizing in Pmc21, formally the highest subgroup of the wurtzite type fulfilling Pauling's rules for 1:1:2 stoichiometries, has been puzzling scientists for a while; a rationalization is given, from a crystallographic basis, of why this space group is unlikely to be adopted.
    Keywords: 548 ; group–subgroup relationships ; nitride materials ; wurtzite type
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  • 31
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-20
    Description: An approach for the comparison of pair distribution functions (PDFs) has been developed using a similarity measure based on cross‐correlation functions. The PDF is very sensitive to changes in the local structure, i.e. small deviations in the structure can cause large signal shifts and significant discrepancies between the PDFs. Therefore, a comparison based on pointwise differences (e.g. R values and difference curves) may lead to the assumption that the investigated PDFs as well as the corresponding structural models are not in agreement at all, whereas a careful visual inspection of the investigated structural models and corresponding PDFs may reveal a relatively good match. To quantify the agreement of different PDFs for those cases an alternative approach is introduced: the similarity measure based on cross‐correlation functions. In this paper, the power of this application of the similarity measure to the analysis of PDFs is highlighted. The similarity measure is compared with the classical Rwp values as representative of the comparison based on pointwise differences as well as with the Pearson product‐moment correlation coefficient, using polymorph IV of barbituric acid as an example.
    Description: A novel approach to the quantification of the agreement between pair distribution functions by a similarity measure based on cross‐correlation functions is introduced and evaluated. image
    Keywords: 548 ; pair distribution functions ; similarity measures ; total scattering techniques ; cross‐correlation functions ; R values
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  • 32
    Publication Date: 2021-06-26
    Description: The high‐precision X‐ray diffraction setup for work with diamond anvil cells (DACs) in interaction chamber 2 (IC2) of the High Energy Density instrument of the European X‐ray Free‐Electron Laser is described. This includes beamline optics, sample positioning and detector systems located in the multipurpose vacuum chamber. Concepts for pump–probe X‐ray diffraction experiments in the DAC are described and their implementation demonstrated during the First User Community Assisted Commissioning experiment. X‐ray heating and diffraction of Bi under pressure, obtained using 20 fs X‐ray pulses at 17.8 keV and 2.2 MHz repetition, is illustrated through splitting of diffraction peaks, and interpreted employing finite element modeling of the sample chamber in the DAC.
    Description: The high‐precision X‐ray diffraction (XRD) setup for work with diamond anvil cells (DACs) in Interaction Chamber 2 of the High Energy Density (HED) instrument of the European X‐ray Free‐Electron Laser is described. image
    Keywords: 548 ; diamond anvil cells ; X‐ray free‐electron lasers ; high‐precision X‐ray diffraction ; finite element modeling
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  • 33
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-26
    Description: The refractive index of a y‐cut SiO2 crystal surface is reconstructed from orientation‐dependent soft X‐ray reflectometry measurements in the energy range from 45 to 620 eV. Owing to the anisotropy of the crystal structure in the (100) and (001) directions, a significant deviation of the measured reflectance at the Si L2,3 and O K absorption edges is observed. The anisotropy in the optical constants reconstructed from these data is also confirmed by ab initio Bethe–Salpeter equation calculations for the O K edge. This new experimental data set expands the existing literature data for quartz crystal optical constants significantly, particularly in the near‐edge regions.
    Description: The refractive index of a y‐cut SiO2 crystal surface is reconstructed from polarization‐dependent soft X‐ray reflectometry measurements in the energy range from 45 to 620 eV. The reconstructed anisotropy in the optical constants is also confirmed by ab initio Bethe–Salpeter equation calculations of the O K edge. image
    Keywords: 548 ; optical constants ; quartz ; anisotropy ; soft X‐ray reflectometry
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  • 34
    Publication Date: 2021-07-05
    Description: Mixed ionic electronic conducting ceramics Nd6−yWO12−δ (δ is the oxygen deficiency) provide excellent stability in harsh environments containing strongly reactive gases such as CO2, CO, H2, H2O or H2S. Due to this chemical stability, they are promising and cost‐efficient candidate materials for gas separation, catalytic membrane reactors and protonic ceramic fuel cell technologies. As in La6−yWO12−δ, the ionic/electronic transport mechanism in Nd6−yWO12−δ is expected to be largely controlled by the crystal structure, the conclusive determination of which is still lacking. This work presents a crystallographic study of Nd5.8WO12−δ and molybdenum‐substituted Nd5.7W0.75Mo0.25O12−δ prepared by the citrate complexation route. High‐resolution synchrotron and neutron powder diffraction data were used in combined Rietveld refinements to unravel the crystal structure of Nd5.8WO12−δ and Nd5.7W0.75Mo0.25O12−δ. Both investigated samples crystallize in a defect fluorite crystal structure with space group Fm3m and doubled unit‐cell parameter due to cation ordering. Mo replaces W at both Wyckoff sites 4a and 48h and is evenly distributed, in contrast with La6−yWO12−δ. X‐ray absorption spectroscopy as a function of partial pressure pO2 in the near‐edge regions excludes oxidation state changes of Nd (Nd3+) and W (W6+) in reducing conditions: the enhanced hydrogen permeation, i.e. ambipolar conduction, observed in Mo‐substituted Nd6−yWO12−δ is therefore explained by the higher Mo reducibility and the creation of additional – disordered – oxygen vacancies.
    Description: The crystal structures of non‐substituted and Mo‐substituted neodymium tungstates are described in detail through neutron diffraction and high‐resolution X‐ray diffraction. Combined X‐ray and neutron diffraction refinements and electron probe micro‐analysis were employed to locate Mo atoms in the crystal structure of Nd6−yW1−zMozO12−δ (z = 0, 0.25), while X‐ray absorption spectroscopy in the near‐edge regions confirmed no changes in the oxidation states of Nd and W.
    Keywords: 548 ; powder diffraction ; mixed conductors ; X‐ray absorption spectroscopy (XAS) ; Nd6−yWO12−δ
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  • 35
    Publication Date: 2021-07-04
    Description: High‐performance numerical codes are an indispensable tool for hydrogeologists when modeling subsurface flow and transport systems. But as they are written in compiled languages, like C/C++ or Fortran, established software packages are rarely user‐friendly, limiting a wider adoption of such tools. OpenGeoSys (OGS), an open‐source, finite‐element solver for thermo‐hydro‐mechanical–chemical processes in porous and fractured media, is no exception. Graphical user interfaces may increase usability, but do so at a dramatic reduction of flexibility and are difficult or impossible to integrate into a larger workflow. Python offers an optimal trade‐off between these goals by providing a highly flexible, yet comparatively user‐friendly environment for software applications. Hence, we introduce ogs5py, a Python‐API for the OpenGeoSys 5 scientific modeling package. It provides a fully Python‐based representation of an OGS project, a large array of convenience functions for users to interact with OGS and connects OGS to the scientific and computational environment of Python.
    Description: German Federal Environmental Foundation http://dx.doi.org/10.13039/100007636
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Keywords: 551.49 ; hydrogeology ; subsurface flow ; modeling ; software
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  • 36
    Publication Date: 2021-06-30
    Description: Niobium metal foils were heat‐treated at 900°C under different conditions and in situ investigated with time‐resolved X‐ray absorption fine‐structure (EXAFS and XANES) measurements. The present study aims to mimic the conditions usually applied for heat treatments of Nb materials used for superconducting radiofrequency cavities, in order to better understand the evolving processes during vacuum annealing as well as for heat treatments in controlled dilute gases. Annealing in vacuum in a commercially available cell showed a substantial amount of oxidation, so that a designated new cell was designed and realized, allowing treatments under clean high‐vacuum conditions as well as under well controllable gas atmospheres. The experiments performed under vacuum demonstrated that the original structure of the Nb foils is preserved, while a detailed evaluation of the X‐ray absorption fine‐structure data acquired during treatments in dilute air atmospheres (10−5 mbar to 10−3 mbar) revealed a linear oxidation with the time of the treatment, and an oxidation rate proportional to the oxygen (air) pressure. The structure of the oxide appears to be very similar to that of polycrystalline NbO. The cell also permits controlled exposures to other reactive gases at elevated temperatures; here the Nb foils were exposed to dilute nitrogen atmospheres after a pre‐conditioning of the studied Nb material for one hour under high‐vacuum conditions, in order to imitate typical conditions used for nitrogen doping of cavity materials. Clear structural changes induced by the N2 exposure were found; however, no evidence for the formation of niobium nitride could be derived from the EXAFS and XANES experiments. The presented results establish the feasibility to study the structural changes of the Nb materials in situ during heat treatments in reactive gases with temporal resolution, which are important to better understand the underlaying mechanisms and the dynamics of phase formation during those heat treatments in more detail.
    Keywords: 548 ; in situ EXAFS ; high temperature ; time‐resolved EXAFS ; niobium
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  • 37
    Publication Date: 2021-06-27
    Description: Transport processes that lead to exchange of mass between surface water and groundwater play a significant role for the ecological functioning of aquatic systems, for hydrological processes and for biogeochemical transformations. In this study, we present a novel integral modeling approach for flow and transport at the sediment–water interface. The model allows us to simultaneously simulate turbulent surface and subsurface flow and transport with the same conceptual approach. For this purpose, a conservative transport equation was implemented to an existing approach that uses an extended version of the Navier–Stokes equations. Based on previous flume studies which investigated the spreading of a dye tracer under neutral, losing and gaining flow conditions the new solver is validated. Tracer distributions of the experiments are in close agreement with the simulations. The simulated flow paths are significantly affected by in‐ and outflowing groundwater flow. The highest velocities within the sediment are found for losing condition, which leads to shorter residence times compared to neutral and gaining conditions. The largest extent of the hyporheic exchange flow is observed under neutral condition. The new solver can be used for further examinations of cases that are not suitable for the conventional coupled models, for example, if Reynolds numbers are larger than 10. Moreover, results gained with the integral solver provide high‐resolution information on pressure and velocity distributions at the rippled streambed, which can be used to improve flow predictions. This includes the extent of hyporheic exchange under varying ambient groundwater flow conditions.
    Description: Technische Universität Berlin, Germany
    Description: German Research Foundation http://dx.doi.org/10.13039/501100001659
    Keywords: 551.4 ; aquatic systems ; sediment-water interface ; transport model
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  • 38
    Publication Date: 2021-03-27
    Description: High‐pressure single‐crystal to 20 GPa and powder diffraction measurements to 50 GPa, show that the structure of Pb2SnO4 strongly distorts on compression with an elongation of one axis. A structural phase transition occurs between 10 GPa and 12 GPa, with a change of space group from Pbam to Pnam. The resistivity decreases by more than six orders of magnitude when pressure is increased from ambient conditions to 50 GPa. This insulator‐to‐semiconductor transition is accompanied by a reversible appearance change from transparent to opaque. Density functional theory‐based calculations show that at ambient conditions the channels in the structure host the stereochemically‐active Pb 6s2 lone electron pairs. On compression the lone electron pairs form bonds between Pb2+ ions. Also provided is an assignment of irreducible representations to the experimentally observed Raman bands.
    Description: The structure of Pb2SnO4 is found to strongly distort on compression and a structural phase transition with a change of space group from Pbam to Pnam occurs at ∼11 GPa. Our complementary DFT‐based calculations show that at ambient conditions, the channels in the structure host the stereochemically active Pb 6s2 lone electron pairs which form bonds between the Pb2+ ions with increasing pressure. image
    Keywords: 548 ; lead stannate (Pb2SnO4) ; density functional theory ; high‐pressure X‐ray diffraction ; pressure‐induced phase transition ; insulator–semiconductor transition
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  • 39
    Publication Date: 2021-07-05
    Description: Sustainable arable cropping relies on repeated liming. Yet, the associated increase in soil pH can reduce the availability of iron (Fe) to plants. We hypothesized that repeated liming, but not pedogenic processes such as lessivage (i.e., translocation of clay particles), alters the Fe cycle in Luvisol soil, thereby affecting Fe isotope composition in soils and crops. Hence, we analysed Fe concentrations and isotope compositions in soil profiles and winter rye from the long‐term agricultural experimental site in Berlin‐Dahlem, Germany, where a controlled liming trial with three field replicates per treatment has been conducted on Albic Luvisols since 1923. Heterogeneity in subsoil was observed at this site for Fe concentration but not for Fe isotope composition. Lessivage had not affected Fe isotope composition in the soil profiles. The results also showed that almost 100 years of liming lowered the concentration of the HCl‐extractable Fe that was potentially available for plant uptake in the surface soil (0–15 cm) from 1.03 (standard error (SE) 0.03) to 0.94 (SE 0.01) g kg−1. This HCl‐extractable Fe pool contained isotopically lighter Fe (δ56Fe = −0.05 to −0.29‰) than the bulk soil (δ56Fe = −0.08 to 0.08‰). However, its Fe isotope composition was not altered by the long‐term lime application. Liming resulted in relatively lower Fe concentrations in the roots of winter rye. In addition, liming led to a heavier Fe isotope composition of the whole plants compared with those grown in the non‐limed plots (δ56FeWholePlant_ + Lime = −0.12‰, SE 0.03 vs. δ56FeWholePlant_‐Lime = −0.21‰, SE 0.01). This suggests that the elevated soil pH (increased by one unit due to liming) promoted the Fe uptake strategy through complexation of Fe(III) from the rhizosphere, which favoured heavier Fe isotopes. Overall, the present study showed that liming and a related increase in pH did not affect the Fe isotope compositions of the soil, but may influence the Fe isotope composition of plants grown in the soil if they alter their Fe uptake strategy upon the change of Fe availability. Highlights Fe concentrations and stocks, but not Fe isotope compositions, were more heterogeneous in subsoil than in topsoil. Translocation of clay minerals did not result in Fe isotope fractionation in the soil profile of a Luvisol. Liming decreased Fe availability in topsoil, but did not affect its δ56Fe values. Uptake of heavier Fe isotopes by graminaceous crops was more pronounced at elevated pH.
    Description: Bundesministerium für Bildung und Forschung http://dx.doi.org/10.13039/501100002347
    Keywords: 551.9 ; liming ; plant‐available Fe pool in soil ; winter rye ; δ56Fe
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  • 40
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-05
    Description: Heterovalent ternary nitrides are considered one of the promising classes of materials for photovoltaics, combining attractive physical properties with low toxicity and element abundance. One of the front‐runner systems under consideration is ZnSnN2. Although it is nominally a ternary compound, no clear crystallographic evidence for cation ordering has been observed so far. An attempt to elucidate this discrepancy [Quayle (2020). Acta Cryst. A76, 410–420] was the trigger for an intensive discussion between the authors, and an agreement was reached to elaborate on some points in order to set things in perspective. Rather than using a conventional comment–answer scheme, this is published in the form of a joint discussion to celebrate constructive criticism and collegiality.
    Description: A scientific exchange on an earlier paper [Quayle (2020). Acta Cryst. A76, 410–420] has led to the clarification of some of the points. image
    Keywords: 548 ; group–subgroup relationships ; nitride materials ; wurtzite type
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  • 41
    Publication Date: 2021-06-26
    Description: X‐SPEC is a high‐flux spectroscopy beamline at the KIT (Karlsruhe Institute of Technology) Synchrotron for electron and X‐ray spectroscopy featuring a wide photon energy range. The beamline is equipped with a permanent magnet undulator with two magnetic structures of different period lengths, a focusing variable‐line‐space plane‐grating monochromator, a double‐crystal monochromator and three Kirkpatrick–Baez mirror pairs. By selectively moving these elements in or out of the beam, X‐SPEC is capable of covering an energy range from 70 eV up to 15 keV. The flux of the beamline is maximized by optimizing the magnetic design of the undulator, minimizing the number of optical elements and optimizing their parameters. The beam can be focused into two experimental stations while maintaining the same spot position throughout the entire energy range. The first experimental station is optimized for measuring solid samples under ultra‐high‐vacuum conditions, while the second experimental station allows in situ and operando studies under ambient conditions. Measurement techniques include X‐ray absorption spectroscopy (XAS), extended X‐ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X‐ray PES (HAXPES), as well as X‐ray emission spectroscopy (XES) and resonant inelastic X‐ray scattering (RIXS).
    Description: X‐SPEC is a high‐flux undulator beamline for electron and X‐ray spectroscopy with an energy range from 70 eV to 15 keV. It offers X‐ray absorption spectroscopy (XAS), extended X‐ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X‐ray PES (HAXPES), as well as X‐ray emission spectroscopy (XES) and resonant inelastic X‐ray scattering (RIXS) for in vacuo, in situ and operando sample environments. image
    Keywords: 548 ; undulator beamline ; soft X‐ray ; tender X‐ray ; hard X‐ray ; in situ ; operando ; HAXPES ; RIXS ; XAS ; XES
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  • 42
    facet.materialart.
    Unknown
    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-06-26
    Description: A method for the ab initio crystal structure determination of organic compounds by a fit to the pair distribution function (PDF), without prior knowledge of lattice parameters and space group, has been developed. The method is called `PDF‐Global‐Fit' and is implemented by extension of the program FIDEL (fit with deviating lattice parameters). The structure solution is based on a global optimization approach starting from random structural models in selected space groups. No prior indexing of the powder data is needed. The new method requires only the molecular geometry and a carefully determined PDF. The generated random structures are compared with the experimental PDF and ranked by a similarity measure based on cross‐correlation functions. The most promising structure candidates are fitted to the experimental PDF data using a restricted simulated annealing structure solution approach within the program TOPAS, followed by a structure refinement against the PDF to identify the correct crystal structure. With the PDF‐Global‐Fit it is possible to determine the local structure of crystalline and disordered organic materials, as well as to determine the local structure of unindexable powder patterns, such as nanocrystalline samples, by a fit to the PDF. The success of the method is demonstrated using barbituric acid as an example. The crystal structure of barbituric acid form IV solved and refined by the PDF‐Global‐Fit is in excellent agreement with the published crystal structure data.
    Keywords: 548 ; pair distribution function analysis ; structure determination ; total scattering technique ; similarity measures ; PDF‐Global‐Fit
    Type: article
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  • 43
    Publication Date: 2021-07-01
    Description: Vibrio species play a crucial role in maintaining the carbon and nitrogen balance between the oceans and the land through their ability to employ chitin as a sole source of energy. This study describes the structural basis for the action of the GH20 β‐N‐acetylglucosaminidase (VhGlcNAcase) in chitin metabolism by Vibrio campbellii (formerly V. harveyi) strain ATCC BAA‐1116. Crystal structures of wild‐type VhGlcNAcase in the absence and presence of the sugar ligand, and of the unliganded D437A mutant, were determined. VhGlcNAcase contains three distinct domains: an N‐terminal carbohydrate‐binding domain linked to a small α+β domain and a C‐terminal (β/α)8 catalytic domain. The active site of VhGlcNAcase has a narrow, shallow pocket that is suitable for accommodating a small chitooligosaccharide. VhGlcNAcase is a monomeric enzyme of 74 kDa, but its crystal structures show two molecules of enzyme per asymmetric unit, in which Gln16 at the dimeric interface of the first molecule partially blocks the entrance to the active site of the neighboring molecule. The GlcNAc unit observed in subsite −1 makes exclusive hydrogen bonds to the conserved residues Arg274, Tyr530, Asp532 and Glu584, while Trp487, Trp546, Trp582 and Trp505 form a hydrophobic wall around the −1 GlcNAc. The catalytic mutants D437A/N and E438A/Q exhibited a drastic loss of GlcNAcase activity, confirming the catalytic role of the acidic pair (Asp437–Glu438).
    Description: Crystal structures of a GH20 β‐N‐acetylglucosaminidase from V. campbellii reveal substrate specificity in chitin utilization.
    Keywords: 577.14 ; GH20 β‐N‐acetylglucosaminidase ; chitin recycling ; Vibrio spp ; marine bacteria
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  • 44
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    Unknown
    American Meteorological Society
    Publication Date: 2020-03-16
    Description: Author Posting. © American Meteorological Society, 2020. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 33(4), (2020): 1535-1545, doi:10.1175/JCLI-D-19-0547.1.
    Description: In a transient warming scenario, the North Atlantic is influenced by a complex pattern of surface buoyancy flux changes that ultimately weaken the Atlantic meridional overturning circulation (AMOC). Here we study the AMOC response in the CMIP5 experiment, using the near-geostrophic balance of the AMOC on interannual time scales to identify the role of temperature and salinity changes in altering the circulation. The thermal wind relationship is used to quantify changes in the zonal density gradients that control the strength of the flow. At 40°N, where the overturning cell is at its strongest, weakening of the AMOC is largely driven by warming between 1000- and 2000-m depth along the western margin. Despite significant subpolar surface freshening, salinity changes are small in the deep branch of the circulation. This is likely due to the influence of anomalously salty water in the subpolar intermediate layers, which is carried northward from the subtropics in the upper limb of the AMOC. In the upper 1000 m at 40°N, salty anomalies due to increased evaporation largely cancel the buoyancy increase due to warming. Therefore, in CMIP5, temperature dynamics are responsible for AMOC weakening, while freshwater forcing instead acts to strengthen the circulation in the net. These results indicate that past modeling studies of AMOC weakening, which rely on freshwater hosing in the subpolar gyre, may not be directly applicable to a more complex warming scenario.
    Description: We acknowledge the World Climate Research Programme’s Working Group on Coupled Modelling, which is responsible for CMIP, and we thank the climate modeling groups (listed in Table 1 of this paper) for producing and making available their model output. We also thank John Marshall for helpful discussions on the driving mechanisms of the AMOC, and three anonymous reviewers whose comments greatly improved the manuscript. This work was supported by NASA Headquarters under the NASA Earth and Space Science Fellowship Program Award 80NSSC17K0372, and by National Science Foundation Award OCE-1433132.
    Description: 2020-07-20
    Keywords: North Atlantic Ocean ; Thermohaline circulation ; Water masses/storage ; Climate change ; Climate prediction ; Climate models
    Repository Name: Woods Hole Open Access Server
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  • 45
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    International Union of Crystallography | 5 Abbey Square, Chester, Cheshire CH1 2HU, England
    Publication Date: 2021-09-29
    Description: The resolution function of a spectrometer based on a strongly bent single crystal (bending radius of 10 cm or less) is evaluated. It is shown that the resolution is controlled by two parameters: (i) the ratio of the lattice spacing of the chosen reflection to the crystal thickness and (ii) a single parameter comprising crystal thickness, its bending radius, distance to a detector, and anisotropic elastic constants of the chosen crystal. The results allow the optimization of the parameters of bent‐crystal spectrometers for the hard X‐ray free‐electron laser sources.
    Description: The resolution function of a bent‐crystal spectrometer for pulses of an X‐ray free‐electron laser is evaluated. Under appropriate conditions, the energy resolution reaches the ratio of the lattice spacing to the crystal thickness. image
    Keywords: 548 ; X‐ray free‐electron lasers ; X‐ray spectroscopy ; bent crystals ; diamond crystal optics ; femtosecond X‐ray diffraction
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  • 46
    Publication Date: 2021-09-29
    Description: To study and control the incoherent inelastic background in small‐angle neutron scattering, which makes a significant contribution to the detected scattering from hydrocarbon systems, the KWS‐2 small‐angle neutron scattering diffractometer operated by the Jülich Centre for Neutron Science (JCNS) at Heinz‐Maier Leibnitz Zentrum (MLZ), Garching, Germany, was equipped with a secondary single‐disc chopper that is placed in front of the sample stage. This makes it possible to record in time‐of‐flight mode the scattered neutrons in the high‐Q regime of the instrument (i.e. short incoming wavelengths and detection distances) and to discard the inelastic component from the measured data. Examples of measurements on different materials routinely used as standard samples, sample containers and solvents in the experiments at KWS‐2 are presented. When only the elastic region of the spectrum is used in the data‐reduction procedure, a decrease of up to two times in the incoherent background of the experimentally measured scattering cross section may be obtained. The proof of principle is demonstrated on a solution of bovine serum albumin in D2O.
    Description: A new chopper has been installed at the sample position in front of the sample stage at the KWS‐2 small‐angle neutron‐scattering diffractometer of the Jülich Centre for Neutron Science. The pulsed beam and the time‐of‐flight data acquisition enable the separation of elastic and inelastic scattering from hydrogenous samples.
    Keywords: 548 ; TOF‐SANS ; incoherent neutron scattering ; inelastic neutron scattering ; hydrocarbon systems
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  • 47
    Publication Date: 2021-09-29
    Description: Coping with the growing impacts of flooding in EU countries, a paradigm shift in flood management can be observed, moving from safety‐based towards risk‐based approaches and holistic perspectives. Flood resilience is a common denominator of most of the approaches. In this article, we present the ‘Flood Resilience Rose’ (FRR), a management tool to promote harmonised action towards flood resilience in European regions and beyond. The FRR is a result of a two‐step process. First, based on scientific concepts as well as analysis of relevant policy documents, we identified three ‘levels of operation’. The first level refers to the EU Floods Directive and an extended multi‐layer safety approach, comprising the four different layers of protection, prevention, preparedness and recovery, and related measures to be taken. This level is not independent but depends both on the institutional (second level) and the wider (third level) context. Second, we used surveys, semi‐structured interviews and group discussions during workshops with experts from Belgium, Denmark, Germany, the Netherlands and the United Kingdom to validate the definitions and the FRR's practical relevance. The presented FRR is thus the result of rigorous theoretical and practical consideration and provides a tool capable to strengthen flood risk management practice.
    Description: European Regional Development Fund http://dx.doi.org/10.13039/501100008530
    Keywords: 551.48 ; flood defence measures ; governance and institutions ; integrated flood risk management ; resilience
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  • 48
    Publication Date: 2021-09-29
    Description: Cubic rare‐earth sesquioxide crystals are strongly demanded host materials for high power lasers, but due to their high melting points investigations on their thermodynamics and the growth of large‐size crystals of high optical quality remain a challenge. Detailed thermal investigations of the ternary system Lu2O3–Sc2O3–Y2O3 revealing a large range of compositions with melting temperatures below 2200°C and a minimum of 2053°C for the composition (Sc0.45Y0.55)2O3 are presented. These reduced temperatures enable for the first time the growth of high optical quality mixed sesquioxide crystals with disordered structure by the conventional Czochralski method from iridium crucibles. An (Er0.07Sc0.50Y0.43)2O3 crystal is successfully grown and characterized with respect to its crystallographic properties as well as its composition, thermal conductivity and optical absorption in the 1 µm range.
    Description: The phase diagram of the ternary system Lu2O3–Sc2O3–Y2O3 is investigated and compositions with melting points below 2200°C are found. This allows for the first successful growth of the mixed cubic sesquioxide crystal (Er0.07Sc0.50Y0.43)2O3 by the Czochralski method from an iridium crucible. image
    Keywords: 548 ; crystal growth ; optical materials ; phase diagrams ; melting points ; rare earth sesquioxides
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  • 49
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract Specimen thickness is the main experimental factor controlling the results of illite crystallinity (IC) or crystallite size measurements on sedimentation slides. Different values obtained from thick and thin preparations are due to grain-size gradation effects, which may exclude larger and higher ordered grains from contributing to the diffraction. Orientation effects control the measured peak intensity. The change from poor particle orientation in thick slides to high orientation in very thin slides is marked by an increase in specimen density, diminishing non-basal reflections, and by a strong increase in peak intensity. A plateau with constant peak breadths is observed if thin slides of well ordered, platy illites are used. A similar plateau can be recognized for thick preparations of specimens from less ordered materials, but not from well ordered ones. Therefore, it is suggested that IC is determined on very thin sedimentation slides with a thickness of 0.25 mg/cm2 or less. Ultrasonic and H2O2 treatments enhance the degree of particle orientation by destruction of grain aggregates and organic compounds, leading to smaller peak breadths and higher intensities.
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  • 51
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract Five basalt samples from the Point Sal ophiolite, California, were examined using HRTEM and AEM in order to compare observations with interpretations of XRD patterns and microprobe analyses. XRD data from ethylene-glycol-saturated samples indicate the following percentages of chlorite in mixed-layer chlorite–smectite identified for each specimen: (i) L2036 ± 50%, (ii) L2035 ± 70 and 20%, (iii) 1A-13 ± 70%, (iv) 1B-42 ± 70%, and (v) 1B-55 = 100%. Detailed electron microprobe analyses show that ‘chlorite’analyses with high Si, K, Na and Ca contents are the result of interlayering with smectite-like layers. The Fe/(Fe + Mg) ratios of mixed-layer phyllosilicates from Point Sal samples are influenced by the bulk rock composition, not by the percentage of chlorite nor the structure of the phyllosilicate.Measurements of lattice-fringe images indicate that both smectite and chlorite layers are present in the Point Sal samples in abundances similar to those predicted with XRD techniques and that regular alternation of chlorite and smectite occurs at the unit-cell scale. Both 10- and 14-Å layers were recorded with HRTEM and interpreted to be smectite and chlorite, respectively. Regular alternation of chlorite and smectite (24-Å periodicity) occurs in upper lava samples L2036 and 1A-13, and lower lava sample 1B-42 for as many as seven alternations per crystallite with local layer mistakes. Sample L2035 shows disordered alternation of chlorite and smectite, with juxtaposition of smectite-like layers, suggesting that randomly interlayered chlorite (〈0.5)–smectite exists. Images of lower lava sample 1B-55 show predominantly 14-Å layers. Units of 24 Å tend to cluster in what may otherwise appear to be disordered mixtures, suggesting the existence of a corrensite end-member having thermodynamic significance.
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  • 52
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract White mica crystallinity studies have been carried out on 90 samples of mudrocks, six of spotted slate, and five of accretionary lapilli tuff from the area around the Berwyn Hills, North Wales. Strain was measured for some of the spotted slate and tuff samples. The metamorphic grade increases from southeast to northwest, with values of the Kübler index varying from 0.64 to 0.20Δ2θ. Metamorphic zonal boundaries follow the strike of bedding and cleavage, but crystallinity values increase into stratigraphically younger rocks on the northwest side of the Berwyn Dome. This effect is attributed mainly to a rapid increase in the thickness of synmetamorphic overburden to the northwest, comprising exposed Silurian turbidites and inferred Lower Devonian non-marine sediments. Strain variations have a more local influence on crystallinity, and lateral variations in the contemporary geothermal gradient cannot be ruled out. However, only with unrealistically high gradients would the need for a thick Lower Devonian component to the overburden be removed. This reasoning implies that the metamorphic peak was coeval with the Acadian (late Caledonian) event, rather than with an early diastathermal event.
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  • 53
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
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  • 54
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    Journal of metamorphic geology 9 (1991), S. 0 
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    Topics: Geosciences
    Notes: Abstract Illite crystallinity (IC) measurements, determination of the proportion of 2M mica-polytypes and organic-matter reflectance measurements establish regional diagenetic/low-grade metamorphic trends for the Taconian and Acadian belts of Gaspé Peninsula.IC varies as a function of many factors besides maximum burial temperature and heating time. Correlation between IC and %2M illite polytypes for the Fortin Group and Temiscouata Formation suggests (i) that the amount of high-grade detrital mica in the samples is low, and (ii) that IC can be used with some confidence as an estimator of regional thermal maturation levels. Correlation of these parameters with available organic reflectance values further supports this assumption. The illites of the Temiscouata and western Fortin groups are mostly phengitic in composition, whereas in the eastern outcrop belt they are more Mg- and Fe-rich (celadonitic), but generally also of lower grade and lower 2M content. The d(060) values for illites measured on the unorientated 〈2-μm fraction of samples fall between 1.502 and 1.503 Å (range: 1.500–1.504 Å), indicating relatively low octahedral occupancy by Mg and Fe (between one-fifth and one-third of the available spaces). Pyrophyllite and paragonite were not detected. Chlorites are Fe-rich and ripidolitic.The IC map for the Acadian belt of the peninsula displays general congruence between IC contours (2200 sample points) and structural trends for the 27,000-km2 area. The highest grades (anchimetamorphic) are associated with the oldest rocks (Honorat and Matapedia groups) exposed in the cores of major anticlines. Anchimetamorphic grades associated with the western outcrop belt of the Lower Devonian Fortin Group require 7–8 km of subsidence to accommodate sufficient thickness of overlying younger rocks (on top of 4–5 km of Fortin Group deep-water clastics) to explain the grades in terms of burial metamorphism assuming a geothermal gradient of 30° C km−1. The lowest-grade diagenetic rocks occupy a large area in the northeastern part of the peninsula, smaller areas in the northwestern part of the Acadian belt, in the centre of Chaleurs Bay synclinorium, and in the Ordovician Mictaw Group. The contact between the Taconian and Acadian belt is marked by a distinct maturation discontinuity. The Grand Pabos fault juxtaposes rocks of contrasting maturation levels (Matapedia Group against Fortin Group) in the west, but shows no maturation offset further east in the Honorat Group. The fault zone limiting the Fortin Group in the north is also associated with a major IC jump.
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  • 55
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
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  • 56
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: Abstract The assemblage muscovite-quartz-staurolite-aluminium silicate-biotite-garnet-chlorite with H2O (SABGC assemblage) is invariant in the K2O-FeO-MgO-Al2O3-SiO2-H2O (KFMASH) system. Such five-phase AFM assemblages should be absent in nature, but reported occurrences from at least ten localities suggest that either the assemblage internally controls μH2O or non-KFMASH components stabilize one or more of the phases.Least-squares regression analysis of minerals from South Royalton and Gassetts, Vermont, USA, demonstrates that subsets of the minerals in single SABGC assemblages from both localities are related by balanced reactions involving water. These results are consistent with the interpretation that the subassemblages fixed μH2O at an arbitrary, specified pressure and temperature. Balanced dehydration reactions also may be written between minerals in the SABGC assemblages and four-phase assemblages from the same outcrops interpreted to have equilibrated at the same pressures and temperatures as the five-phase assemblages. These results suggest that different specimens from the same outcrops equilibrated at different values of μH2O, supporting the conclusion that μH2O was not controlled externally. We could not demonstrate internal control of fo2 using measured mineral compositions because oxygen balance occurred in all reactions derived by regression.Regression analysis of published mineral compositions from New Mexico failed to identify balanced reactions involving water or oxygen either among the phases in a single SABGC assemblage or between SABGC and nearby four-phase assemblages. These results demonstrate that neither μH2O nor fo2 were fixed by the SABGC assemblages at these localities, and permit the interpretations that the assemblages were stabilized by the non-KFMASH components Na or Ca and that μH2O and fo2 were controlled externally.
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  • 57
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: Abstract Albite porphyroblasts are widely distributed in pelitic and semi-pelitic schists of the Fleur de Lys Supergroup, western Newfoundland. Textures and mineral assemblages indicate that albite grew during nearly isothermal decompression from P-T conditions of about 500° C, 9 kbar, to conditions of 550° C, 6.5 kbar. Three compositional varieties of albite-bearing schists, here termed PMAQ (paragonite-muscovite-albite-quartz), MMAQ (microcline-muscovite-albite-quartz), and PMMQ (paragonite-muscovite-margarite-quartz), can be distinguished on the basis of pre-porphyroblast mineral assemblages. Analysis of these assemblages in terms of the composition of the coexisting fluid [log a(Na+/H+) versus log a(K+/H+)] suggests that, as pressure and temperature changed, the stability field of albite expanded at the expense of coexisting matrix phyllosilicates. This promoted growth of albite on pre-existing or newly formed nuclei. Late oligoclase in PMAQ and PMMQ samples is associated with replacement of matrix garnet by plagioclase + mica ° Chlorite, particularly in strongly sheared samples.
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  • 58
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    Journal of metamorphic geology 9 (1991), S. 0 
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    Topics: Geosciences
    Notes: Abstract Spinel-quartz-cordierite and spinel-quartz are found as relic prograde assemblages in Fe-rich granulites from the Araku area, Eastern Ghats belt, India. Subsequent reactions produced orthopyroxene + sillimanite in the former association and garnet + sillimanite in the latter. The first reaction is univariant in the FMAS system, but is trivariant in the present case because of the presence of Zn and Fe3+ in spinel. The second reaction also has high variance because of Zn and Fe3+, but also because of the presence of Ca in garnet. Thermobarometry shows that the metamorphic conditions were approximately 950° C and 8.5 kbar and the fo2 was near the NNO buffer. In Fe-rich bulk compositions and low-P-high-T conditions of metamorphism, two of the univariant reactions around the invariant point [Sa], namely (Sa, Hy) and (Sa, Cd), change topology due to reverse partitioning of Fe-Mg between coexisting garnet and spinel. An alternative partial petrogenetic grid in the system FMAS is constructed for such conditions and is applied satisfactorily to several sapphirine-free spinel granulites. It is shown that bulk composition (XFe and Zn) exerts greater control on the stability of spinel + quartz than fo2. The effect of the presence of Zn and Fe3+ in spinel on the proposed grid is evaluated. Reaction textures in the Araku spinel granulites can be explained from the petrogenetic grid as due to near-isobaric cooling.
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  • 59
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    Journal of metamorphic geology 9 (1991), S. 0 
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    Topics: Geosciences
    Notes: The impure marbles of the internal Sesia-Lanzo Zone underwent a multi-stage metamorphic evolution of Alpine age and retain early-Alpine eclogitic assemblages, partially recrystallized under blueschist to greenschist facies conditions. These high-P assemblages consist of carbonates, phengite, quartz, omphacite, grossular-rich (locally spessartinic) garnet, zoisite and Al-rich titanite. Retrogressive stages are characterized by the growth of glaucophane, paragonite, phlogopite, tremolite and albite. Halogen-rich biotite and amphibole are also present. P-T estimates of the early-Alpine metamophism have been calculated from these unique high-P assemblages, in order to test the applicability of some calibrations to impure carbonate systems. In particular, some Gt-Cpx calibrations and the phengite geobarometer give results (T= 575 ± 45° C at 15 kbar for the eclogitic climax and T≤ 500° C at PH2O ≤ 9 kbar for early-Alpine retrogressive stages) which are within the range obtained from the surrounding lithologies.Phase relationships in P-T-XCO2 space indicate that mineral assemblages in the impure marbles coexisted with H2O-rich fluids (XCO2 〈0.03) during their entire Alpine evolution.
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  • 60
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    Journal of metamorphic geology 8 (1990), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Analysis of the precision of the illite ‘crystallinity’technique shows that machine errors are 〈5%, while intra- and inter-sample errors are variable but are up to 12% and 14%, respectively (1σ). Consideration of this error analysis shows that the isocryst approach, which involves close contouring (e.g. 0.03 Δ2°) of illite ‘crystallinity’data, has a very low degree of confidence (〈0.5) and thus is not regarded as statistically valid. If contouring is to be undertaken with a high degree of confidence (〉0.8) it is necessary that contours should be at intervals of 0.1 ΔΘ2°, which is equivalent to subdivision of the anchizone into upper and lower units. Where previous interpretations have relied upon an isocryst method of contouring at less than 0.1 ΔΘ2° the conclusions must be regarded as unsubstantiated.Centrifuge separation of clay fractions (based on a Stokes’law application) gives separations in which a significant, but variable, percentage of grains have long axes greater than the size calculated. For the typical 〈2-μm fraction utilized, some 20% of grains lie in the 2–4-μm range, although the proportion is not believed to have a significant effect upon ‘crystallinity’values. The formula is applicable for grain-sizes down to 0.5 μm. Illite ‘crystallinity’values on samples prepared by an ultrasonic disaggregation method show a small increase on those prepared by ball mill crushing. The differences are minimal at the epi/anchizone level but increase to some 10% at the anchizone/diagenetic level. The effect on grade determinations is again thought to be minimal and indicates that concern over unsuitability of the ultrasonic disaggregation method is unfounded.
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  • 61
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    Journal of metamorphic geology 8 (1990), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
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  • 62
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    Journal of metamorphic geology 8 (1990), S. 0 
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    Topics: Geosciences
    Notes: The amphibolite facies Puolankajärvi Formation (PjF) occupies the western margin of the Early Proterozoic Kainuu Schist Belt (KSB) of northern Finland. The lower and middle parts of the PjF consist of turbiditic psammites and pelites and tempestitic semipelites. This report concentrates on the pelitic lithologies which include quartz–two-mica–plagioclase schists with variable amounts of garnet, staurolite, andalusite and biotite porphyroblasts as well as sillimanite and cordierite segregations.The KSB forms a major north–south-trending synclinorium between two Archaean blocks. It contains both autochthonous and allochthonous units and is cut by faults and shear zones. The PjF lies on the western side of the KSB and is probably allochthonous. The formation has undergone six major deformation phases (D1, D2, D3a, D3b, D4 and D5). During D3a-D5 the maximum principal stress (σ1) changed in a clockwise direction from south-west to north-east. Between D2 and D3 the intermediate principal stress (σ2) changed from horizontal to vertical and the interval between D2 and D3 marks a transition from thrust to strike-slip tectonics.Relict structures in the porphyroblasts indicate the following mineral growth–deformation evolution in the PjF. (1) Throughout the PjF there was a successive crystallization of garnet (syn-D1), poryphyroblastic biotite (inter-D3/4) and staurolite (inter-D3/4) during the pre-D4 stage. (2) A syn-D4-inter-D4/5 crystallization of kyanite, sillimanite (fibrolite), porphyroblastic tourmaline, magnetite, rutile, cordierite and muscovite–biotite–plagioclase pseudomorphs after staurolite was most localized at and near D4 shear zones. (3) A syn- to post-D5 generation of andalusite, ilmenohematite and sheet silicates after staurolite and after cordierite occurred near D5 faults.The evolution outlined here permits the relative dating of the PjF parageneses, which is used in the second part of the study (Tuisku & Laajoki, 1990), and, together with the knowledge of the pressure–temperature conditions during various growth events, makes it possible to compile pressure–temperature–deformation paths for the PjF.
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Petrographical and mineral chemical data are given for the eclogites which occur in the garnet-kyanite micaschists of the Penninic Dora-Maira Massif between Brossasco, Isasca and Martiniana (Italian Western Alps) and for a sodic whiteschist associated with the pyrope-coesite whiteschists of Martiniana. The Brossasco-Isasca (BI) eclogites are fine grained, foliated and often mica-rich rocks with a strong preferred orientation of omphacite crystals and white micas. Porphyroblasts of hornblende are common in some varieties, whilst zoisite and kyanite occur occasionally in pale green varieties associated with leucocratic layers with quartz, jadeite and garnet. These features differentiate the BI eclogites from the eclogites that occur in other continental units of the Western Alps, which all belong to type C. Garnet, sodic pyroxene and glaucophane are the major minerals in the sodic whiteschist.Sodic pyroxene in the eclogites is an omphacite often close to Jd50Di50, with very little acmite and virtually no AlIV, and impure jadeite in the leucocratic layers and in the sodic whiteschist. Garnet is almandine with 20–30 mol. % for each of the pyrope and grossular components in the eclogites and a pyrope-rich variety in the sodic whiteschist. White mica is a variably substituted phengite, and paragonite apparently only occurs as a replacement product of kyanite. Amphibole is hornblende in the eclogites, but the most magnesian glaucophane yet described in the sodic whiteschist. Quartz pseudomorphs of coesite were found occasionally in a few pyroxenes and garnets.The P-T conditions during the VHP event are constrained in the eclogites by reactions which define a field ranging from 27–28 kbar to 35 kbar and from 680 to 750° C. These temperatures are consistent with the results of garnet-pyroxene and garnet-phengite geothermometry which suggest that the eclogites may have equilibrated at around 700° C. In the sodic whiteschist pressures ranging from 29 to 35 kbar can be deduced from the stability of the jadeite-pyrope garnet-glaucophane compatibility. As in the eclogites water activity must have been low. Such conditions are close to the P-T values estimated for the early Alpine recrystallization of the pyrope-coesite rock and, like petrographical and mineralogical features, set aside the BI eclogites from the other eclogites of the Western Alps, instead indicating a close similarity to some of the eclogite bodies occurring in the Adula nappe of the Central Alps. An important corollary is that glaucophane stability, at least in Na- and Mg-rich compositions and under very high pressures, may extend up to 700° C, in agreement with the HT stability limit suggested by experimental studies.
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  • 64
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    Journal of metamorphic geology 9 (1991), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: The retrograde P-T trajectory of the eclogitic Fe-Ti-gabbros from the Ligurian Alps is constrained by the appearance of mineral parageneses post-dating the Na-clinopyroxene + garnet eclogitic assemblage and indicating the following sequence of metamorphic events: (1) amphibolitic stage— edenite/katophorite + plagioclase (An33–43) + oxides in symplectitic aggregates; (2) glaucophanic stage— a porphyroblastic glaucophanic amphibole has overgrown the symplectite, winchite also occurs as thin rims around glaucophane and both amphiboles are, sometimes, armoured by atoll garnets; (3) albite-amphibolite stage—barroisite/katophorite + albite + epidote + oxides ± chlorite overprint the glaucophanic stage minerals; (4) greenschist stage—represented by actinolite + albite + epidote + oxide paragenesis.The metamorphic evolution is complex and the decompression path, on a P–T diagram, is significantly different from those defined in the literature for the Voltri eclogites. The main features inferred from the P–T path are the following: (1) the pressure climax does not match the thermal climax, the maximum temperature conditions are in fact achieved during the early stage of uplift; (2) a decrease in temperature, suggested by the appearance of glaucophane after the amphibolitic symplectite; (3) successive uplift, probably accompanied by an increase in temperature. The complexity of the P-T path drawn for the Voltri eclogites can be explained with a mechanism of successive underthrusts propagating from the innermost to the outermost sector of the Ligurian Alps.
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  • 65
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    Journal of metamorphic geology 8 (1990), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Within the Çokkul synform, Caledonian metamorphic rocks of the Middle Köli Nappe Complex (MKNC) are in low-angle fault contact with the basement mylonites derived from the Precambrian Tysfjord granite-gneiss. In the synform, the MKNC is composed of four fault-bounded nappes each of which has a distinct tectonic stratigraphy composed of amphibolite-facies metamorphosed pelitic and psammitic schists with minor lensoidal bodies of mafic and ultramafic rocks.Pelitic rocks from the three structurally lowest nappes contain the low-variance AFM mineral assemblages gar + bio + staur and staur + ky + bio with mu + qtz + ilm, whereas staur and ky are absent from the highest nappe, the Kallakvare nappe. AFM mineral assemblages in the three lowest nappes indicate peak metamorphic temperatures of 610–660°C and peak pressures in excess of 600 MPa. Mineral assemblages from the Kallakvare nappe are not as diagnostic of metamorphic grade. However, rocks from that nappe contain coexisting plagioclases from both sides of the peristerite gap, suggesting lower-grade peak P–T conditions than those of the structurally lower nappes. In addition, biotite from the lower nappes is more Ti-rich than biotite from the Kallakvare nappe. However, gar–bio–mu–plag and gar–bio–ky–plag–qtz thermobarometry suggests that all four nappes equilibrated at approximately 525 ± 25°C and 700 ± 100 MPa.Gibbs method thermodynamic modelling of garnet zoning profiles suggests that the lower three nappes followed clockwise P–T paths that involved heating and compression to a metamorphic peak of approximately 575–625°C, 800 MPa followed by cooling and decompression to 525°C, 700 MPa. P–T paths calculated for the Kallakvare nappe show decompression and minor heating to a peak T of 500–525°C. In the lower nappes, staur and ky grew during the heating phase not seen by the highest nappe. The outer parts of the paths from all four nappes are approximately parallel, possibly recording the emplacement of the Kallakvare nappe onto the already stacked lower three nappes at some time following the metamorphic peak. These P–T paths suggest that the sole fault of the Kallakvare nappe is a normal fault. Garnet zonation thus appears to record a previously unrecognized phase of uplift and tectonic thinning of the MKNC. This event appears to be restricted to the MKNC and to have occurred prior to the emplacement of the MKNC onto the Tysfjord granite-gneiss basement of Baltoscandia under greenschist-facies conditions. It may have been responsible for the uplift and cooling of the MKNC from 25–30 km amphibolite-facies conditions prior to its emplacement onto Baltoscandia under 15–20 km greenschist-facies conditions.The deformation zone associated with this normal fault is relatively narrow, generally less than 1 m thick. If this is typical of other detachment faults in the metamorphic infrastructure of the Scandinavian Caledonides, they may be relatively common, but not often recognized due to the detailed study needed to document them.
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  • 66
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    Journal of metamorphic geology 8 (1990), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Numerical models of the progressive evolution of pelitic schists in the NCMnKFMASH system with the assemblage garnet + biotite + chlorite ± staurolite + plagioclase + muscovite + quartz + H2O are presented with the goal of predicting compositional changes in garnet and plagioclase along different P-T paths. The numerical models support several conclusions that should prove useful for interpreting the P-T paths of natural parageneses: (i) Garnet may grow along P-T vectors ranging from heating with decompression to cooling with compression. P-T paths deduced from garnet zoning that are inconsistent with these growth vectors are self-contradictory. (ii) There is a systematic relation between garnet and plagioclase composition and growth such that for most P-T paths, garnet growth requires plagioclase consumption. Furthermore, mass balance in a closed system requires that as plagioclase is consumed the remaining plagioclase becomes increasingly albitic. Inclusions of plagioclase in the core of garnet should be more anorthitic than those near the rim and zoned matrix plagioclase should have rims that are more albitic than the cores. Complex plagioclase textures may arise from the local variability of growth and precipitation kinetics. (iii) A decrease of Fe/(Fe + Mg) in a garnet zoning profile is a reliable indicator of increasing temperature for the assemblage modelled. However, there is no single reliable ΔP monitor and inferences about ΔP can only be made by considering plagioclase and garnet together. (iv) Consumption of garnet during the production of staurolite removes material from the outer shell of a garnet and may make recovery of peak metamorphic compositions and P-T conditions impossible. Low ‘peak’temperatures typically recorded by staurolite-bearing assemblages may reflect this phenomenon. (v) Diffusional homogenization of garnet affects the computed P-T path and results in a clockwise rotation of the computed P-T vector relative to the true P-T path.
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  • 67
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    Topics: Geosciences
    Notes: Abstract Geological relationships and geochronological data suggest that in Miocene time the metamorphic core of the central Himalayan orogen was a wedge-shaped body bounded below by the N-dipping Main Central thrust system and above the N-dipping South Tibetan detachment system. We infer that synchronous movement on these fault systems expelled the metamorphic core southward toward the Indian foreland, thereby moderating the extreme topographic gradient at the southern margin of the Tibetan Plateau. Reaction textures, thermobarometric data and thermodynamic modelling of pelitic schists and gneisses from the Nyalam transect in southern Tibet (28°N, 86°E) imply that gravitational collapse of the orogen produced a complex thermal structure in the metamorphic core. Amphibolite facies metamorphism and anatexis at temperatures of 950 K and depths of at least 30 km accompanied the early stages of displacement on the Main Central thrust system. Our findings suggest that the late metamorphic history of these rocks was characterized by high-T decompression associated with roughly 15 km of unroofing by movement on the South Tibetan detachment system. In the middle of the metamorphic core, roughly 7–8 km below the basal detachment of the South Tibetan system, the decompression was essentially isothermal. Near the base of the metamorphic core, roughly 4–6 km above the Main Central thrust, the decompression was accompanied by about 150 K of cooling. We attribute the disparity between the P–T paths of these two structural levels to cooling of the lower part of the metamorphic core as a consequence of continued (and probably accelerated) underthrusting of cooler rocks in the footwall of the Main Central thrust at the same time as movement on the South Tibetan detachment system.
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  • 68
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: Abstract Metre-scale amphibolite boudins in the Cheyenne Belt of south-eastern Wyoming are cut and deformed by shear zones which preserve a full strain transition across 7 cm, from relatively undeformed amphibolite with a relict igneous texture to mylonitic amphibolite with an L-S tectonic fabric. The strain transition is marked by the progressive rotation of amphibole + plagioclase aggregates into parallelism with the shear-zone boundary. An increase in strain magnitude is indicated by development of the tectonic fabric and progressive reduction of amphibole and plagioclase grain size as a result of cataclasis. Bulk chemistry of five samples across a single strain transition shows no significant or systematic variation in major element chemistry except for a minor loss of SiO2, which indicates that the shear zone was a system essentially closed to non-volatile components during metamorphism and deformation. Amphibolites throughout the shear zone consist of amphibole and plagioclase with only minor amounts of quartz, chlorite, epidote, titanite and ilmenite. Within the relatively undeformed amphibolite, amphibole and plagioclase have wide compositional ranges in single thin sections. Amphibole compositions vary from actinolitic hornblende to magnesio-hornblende with increases in Al, Fe, Na and K contents and decreases in Si and Mg that can be modelled as progress along tschermakite, edenite and FeMg-1 exchange vectors from tremolite. Plagioclase ranges from An60 in cores to An30 within grain-boundary domains. With increasing strain magnitude, local variation of amphibole composition decreases as amphibole becomes predominantly magnesio-hornblende. Plagioclase composition range also decreases, although grain-boundary domains still have higher albite content. These petrological data indicate that shear-zone metamorphism was controlled by the magnitude of strain during synmetamorphic deformation. SEM and microprobe imaging indicate that chemical reactions occurred by a dissolution and reprecipitation process during or after cataclastic deformation. This suggests that grain-boundary formation was an important process in the petrological evolution of the shear zone, possibly by providing zones for fluid ingress to facilitate metamorphic reactions. These results highlight the necessity for conducting detailed microstructural evaluation of rocks in order to interpret petrological, isotopic and geochronological data.
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  • 69
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract Ten metamorphic domains can be distinguished in China, comprising four cratonic, three intracratonic and three intercratonic domains. Each domain contains one or more metamorphic belts, each of which, in turn, contains a characteristic metamorphic facies or facies series that was formed during a distinct metamorphic epoch.The metamorphic domains reflect the tectonic domains and tectonic evolution of China. Ancient continental nucleii in the North China and Tarim–Alxa cratons were probably unified with the Yangtze craton during the Early Proterozoic to form the China Platform. Widespread greenschist facies metamorphism, during the Middle and Late Proterozoic, accompanied by glaucophane–greenschist facies metamorphism, represents a rifting and closure event in the China Platform; a second rifting and closure event in the China Platform occurred during the Caledonian. The China and Siberian platforms were closed during the Hercynian to form the Eurasian Continent. Closure of the ancient Tethys Ocean occurred in the Indosinian epoch, and subduction and collision within Xizang (Tibet) and Taiwan occurred during Mesozoic–Cenozoic time.The distribution in time of types of metamorphism in China suggests cyclical changes of metamorphism known as the Archaean, Proterozoic and Phanerozoic megacycles. Each megacycle since the Archaean consists of a change from progressive, low- to intermediate-grade metamorphism to lower grade, greenschist metamorphism that was superimposed on a general trend in which high-grade metamorphism became progressively less important with time. The change in metamorphic megacycles shows a general secular decrease in regional heat supply during metamorphism punctuated by episodic high-grade, progressive metamorphism within orogenic belts.
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The Shangdan fault in the Qinling Orogenic Belt of China is an important boundary between the Caledonian North Qinling Fold Belt and the Hercynian South Qinling Fold Belt. In the Danfeng area, the fault zone strikes WNW–ESE and comprises four strongly deformed zones and three weakly deformed domains parallel to each other. The fault zone has a complex history of multiple deformation and each domain has a different tectonic style that was formed at different stages of the deformation.The rocks exposed in the weakly deformed domains belong to the Qinling, Danfeng and Liuling Groups. In this paper, the mineral chemistry and mineral assemblages are used to infer the metamorphic conditions and the P–T paths of these units. The metamorphic units in and near the fault zone have different metamorphic conditions and histories that are correlated with the tectonic evolution of the fault zone. Caledonian–Hercynian uplift and southward thrusting of the Proterozoic Qinling Group, over the Danfeng and the Liuling Groups, produced the main metamorphic and tectonic features of the fault zone. Folding of both the Liuling Group and the thrust faults during the Hercynian–Indosinian was accompanied by northward thrusting.
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  • 71
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    Journal of metamorphic geology 12 (1994), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: The intracrystalline diffusion rate of oxygen in diopside was constrained based on natural isotopic variations from a granulite facies marble from Cascade Slide, Adirondacks (New York, USA). The oxygen isotope compositions of the diopsides, measured as a function of grain size, are nearly constant (20.9 ± 0.3‰ vs. SMOW) over the entire measured size range (0.3–3.2 mm diameter). The δ18O values of the cores of calcite grains are 23.0‰. Temperature estimates based on the Δ18O(calcite-diopside) are 800d̀C, in agreement with the highest previous thermometric estimates for these rocks.The lack of isotopic variation in the diopsides as a function of grain size requires that the oxygen intracrystalline diffusion rate in diopside from the Adirondack samples was very slow. The maximum diffusion rates (D800d̀C parallel to the c-axis) were calculated with an infinite reservoir model (IRM) and a finite reservoir model (FRM) that incorporates mineral modal abundances and initial isotopic variations. For an assumed activation energy (Q) = 100 kJ/mol, the IRM diffusion rate estimate of 1.6 times 10-20cm2/s is two orders of magnitude faster than from the FRM; at Q=500kJ/mol, the D800d̀C estimate for both methods is c. 5.6 times 10-20 cm2/s. The present results require that a hydrothermal fluid significantly enhances the diffusion rate of oxygen in diopside if previous data are correct.The δ18O(SMOW) and δ13C(PDB) values of the calcite, measured in situ with a CO2 laser, are 22.9 ± 0.3, 0.1±0.3‰ in the grain cores, 22.1 ±0.3, 0.2 ±0.1‰ at the grain boundaries and 21.7 ±0.4, -0.6±0.1‰ abutting diopside grains. The δ18O and δ13δC values measured conventionally are: crystal cores, 22.96, -0.95‰; abutting diopside grains, 22.38, -0.93‰; bulk, 22.79, -0.95%. Use of the bulk δ18O(calcite) values for thermometry yields unreasonably high temperatures. The lower δ18O values at the calcite grain boundaries are not due to retrograde diffusional exchange with the diopside, they are thought to be a result of a late retrograde fluid infiltration.
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  • 72
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract Discontinuous ultramylonite zones cut Proterozoic granulite facies gneisses in MacRobertson Land, east Antarctica, and preserve evidence of ductile non-coaxial flow and reverse sense of shear. Cross-cutting relationships indicate that ultramylonite deformation involved overthrusting to the east, but progressively rotated to involve overthrusting to the north; rotation of the principal compressive stress axes is inferred. Extensive pseudotachylite developed during ultramylonitization, the history of individual ultramylonite zones having involved a single episode of pseudotachylite generation. Neoblastic sillimanite indicates ultramylonitization occurred at 〉520° C. On the basis of inferred recrystallized granulite facies mineral assemblages ultramylonitization occurred at 〉700° C, and ≤7.3 ± 0.5 kbar, at aH2O± 0.3 and low aCO2. Comparison of these values with those suggested by metamorphic assemblages in rocks unaffected by mylonitization indicates that the Rayner Complex experienced a late increase in pressure of 1–2 kbar during ultramylonitization. The P-T-aH2O conditions of the ultramylonite zones are inferred to have been close to the solidus for minimum melting, pseudotachylite generation having involved a limited pressure drop during brittle fracturing at high strain rates. Most of the pseudotachylite veins are undeformed; the mechanism(s) of fracturing and melting must have caused strain hardening in rocks surrounding the ultramylonite, further strain having been mostly accommodated by a new or subsidiary shear zone. Renewed stress at reduced strain rates, or renewed stress in zones in which the proportion of pseudotachylite was significantly higher, could have led to the rare occurrences of deformed pseudotachylite. The preservation of fine-grained pseudotachylite is dependent on it remaining dry.
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract C-O-H fluid produced by the equilibration of H2O and excess graphite must maintain the atomic H/O ratio of water, 2:1. This constraint implies that all thermodynamic properties of the fluid are uniquely determined at isobaric-isothermal conditions. The O2, H2O and CO2 fugacities (fo2, fH2O and fCO2) of such fluids have been estimated from equations of state and fit as a function of pressure and temperature. These fugacities can be taken as characteristic for graphitic metamorphic systems in which the dominant fluid source is dehydration, e.g. pelitic lithologies. Because there are no compositional degrees of freedom for graphite-saturated fluids produced entirely by dehydration, the variance of the dehydration process is not increased in comparison with that in non-graphitic systems. Thus, compositional ‘buffering’of C-O-H fluids by dehydration equilibria, a common petrological model, requires that redox reactions, decarbonation reactions or external, H/O ± 2, fluid sources perturb the evolution of the metamorphic system. Such perturbations are not likely to be significant in metapelitic environments, but their tendency will be to increase the fO2 of the fluid phase. At high metamorphic grades, pyrite desulphidation reactions may cause a substantial reduction of fH2O and slight increases in fO2 and fCO2 relative to sulphur-free fluid. At low metamorphic grade, sulphur solubility in H/O ± 2 fluids is so low that pyrite decomposition must occur by sulphur-conserving reactions that cause iron depletion in silicates, a common feature of sulphidic pelites. With increasing temperature and sulphur solubility, pyrite desulphidation may be driven by dehydration reactions or infiltration of H2O-rich fluids. The absence of magnetite and the assemblages carbonate + aluminosilicate or pyrite + pyrrhotite + ilmenite from most graphitic metapelites is consistent with an H/O = 2 model for GCOH(S) fluid. For graphitic rocks in which such a model is inapplicable, a phase diagram variable that defines the H/O ratio of GCOH(S) fluid is more useful than the conventional fO2 variable.
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract Muscovite-poor pelitic schists in the wallrocks of the Proterozoic Annex sulphide deposit, near Prieska, South Africa, contain peak metamorphic assemblages including Crd + Bt + Sil, St + Sil + Bt, Crd + St + Bt and, rarely, Ky + St ° Crd. All rocks include oligoclase, quartz and commonly Fe–Mn garnet, with or without muscovite. Peak assemblages, assigned to M2 regional metamorphism in the Gordonia Belt (Namaqua Province), are syn- to post-kinematic with respect to the main S2 fabric although larger staurolite grains contain S1 inclusion trails. Garnet–biotite thermometry, utilizing corrections for Fe3+, Mn, AlVI and Ti, yields peak temperatures of 571–624°C at pressures of 4.5–6.0 kbar. Consideration of the sympathetic variation of XMn in garnet with XMg in biotite and the preserved zoning patterns in prograde garnets, together with the inferred prograde transition from kyanite to sillimanite, indicates that heating occurred during mild decompression to the M2 metamorphic peak. Sillimanite and cordierite grew last in the prograde sequence, possibly related to a pulse of thermal metamorphism (M3) that is found along the margin of the Keimoes Suite batholith to the north.Retrograde assemblages, including Ms + Ky + Chl + Qtz (after Crd + Bt), Ky + Ms (after Sil) and Chl + Ms (after St) indicate a period of isobaric cooling (M4a) terminated by rehydration in the kyanite stability field at about 500°C.The size difference between prograde (1–2-mm) and retrograde (0.05–0.1-mm) mineral grains indicates substantial undercooling below equilibrium positions of relevant retrograde reactions prior to rehydration, and explains why cordierite that grew during M2 is almost completely destroyed. Post-M4a regrowth of staurolite and garnet (M4b) is spatially linked to sites of M4a rehydration. It reached temperatures of 510–530°C, remaining within the stability field of kyanite.A best fit of the observed textural history to the Namaqua orogenic cycle involves collision and heating (M2/D2) followed by granite intrusion (M3), rifting (M4a) and renewed heating due to crustal loading during volcanism (M4b). The P–T path for the Annex region is consistent with those derived from elsewhere in the Gordonia Belt and, with modification, to that published already for the nearby Prieska Copper Mines.
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: Abstract Portions of three Proterozoic tectonostratigraphic sequences are exposed in the Cimarron Mountains of New Mexico. The Cimarron River tectonic unit has affinities to a convergent margin plutonic/volcanic complex. Igneous hornblende from a quartz diorite stock records an emplacement pressure of 2–2.6 kbar. Rocks within this unit were subsequently deformed during a greenschist facies regional metamorphism at 4–5 kbar and 330 ± 50° C.The Tolby Meadow tectonic unit consists of quartzite and schist. Mineral assemblages are indicative of regional metamorphism at pressures near 4 kbar and temperatures of 520 ± 20° C. A low-angle ductile shear zone separates this succession from gneisses of the structurally underlying Eagle Nest tectonic unit. Gneissic granite yields hornblende pressures of 6–8 kbar. Pelitic gneiss records regional metamorphic conditions of 6–7 kbar and 705 ± 15° C, overprinted by retrogression at 4 kbar and 530 ± 10° C. Comparison of metamorphic and retrograde conditions indicates a P–T path dominated by decompression and cooling. The low-angle ductile shear zone represents an extensional structure which was active during metamorphism. This extension juxtaposed the Tolby Meadow and Eagle Nest units at 4 kbar and 520° C. Both units were later overprinted by folding and low-grade metamorphism, and then were emplaced against the Cimarron River tectonic unit by right-slip movement along the steeply dipping Fowler Pass shear zone.An argon isotope-correlation age obtained from igneous hornblende dates plutonism in the Cimarron River unit at 1678 Ma. Muscovite associated with the greenschist facies metamorphic overprint yields a 40 Ar/39 Ar plateau age of 1350 Ma. By contrast, rocks within the Tolby Meadow and Eagle Nest units yield significantly younger argon cooling ages. Hornblende isotope-correlation ages of 1394–1398 Ma are interpreted to date cooling during middle Proterozoic extension. Muscovite plateau ages of 1267–1257 Ma appear to date cooling from the low-grade metamorphic overprint. The latest ductile movement along the Fowler Pass shear zone post-dated these cooling ages. Argon released from muscovites of the Eagle Nest/Tolby Meadow composite unit, at low experimental temperatures, yields apparent ages of c. 1100 Ma. Similar ages are not obtained north-east of the Fowler Pass shear zone, suggesting movement more recently than 1100 Ma.
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: Abstract Regional metamorphism in central Inner Mongolia has occurred during four different periods: the middle Proterozoic, the early Palaeozoic, the middle Palaeozoic and the late Palaeozoic tectonic cycles. The middle Proterozoic and late Palaeozoic metamorphic events are associated with rifting and are characterized by low-pressure facies series. The early Palaeozoic metamorphism occurred in two stages: (1) subduction zone metamorphism resulted in paired metamorphic belts in the Ondor Sum ophiolite and Bainaimiao island arc complex; and (2) orogenic metamorphism occurred during the collision of an island arc with the continent. Two types of middle Palaeozoic metamorphism are represented: (1) subduction zone metamorphism, which affected the melange; and (2) orogenic metamorphism that resulted from continent–continent collision.
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The metamorphic history and tectonic evolution of the Qinling Complex is divided into formation and modification stages. During the Proterozoic formation stage, three deformational sequences are recognized. Andalusite–muscovite, sillimanite–muscovite and sillimanite–K-feldspar zones of amphibolite facies regional metamorphism are earlier than, or synchronous with the first or second phase of folding. Ductile shear zones were formed and Caledonian granites were emplaced during the modification stage. The granites superimposed contact aureoles (garnet–K-feldspar zone) on the regional metamorphic fabric.Metamorphic reactions, P–T conditions of metamorphism and P–T–t paths were estimated by analysis of mineral textures and standard thermobarometric techniques. The P–T–t path of the Proterozoic tectonometamorphic cycle shows prominent clockwise decompression. The P–T–t path of the Caledonian tectonometamorphic cycle is characterized by an early rise of pressure and temperature, followed by isothermal decompression (rapid uplift) and finally with isobaric cooling.The P–T–t paths of the two tectonometamorphic cycles reflect two major stages of collision and uplift in the evolution of the Qinling orogenic belt during the Proterozoic and Caledonian–Hercynian periods, respectively.
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  • 79
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    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
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    Topics: Geosciences
    Notes: Abstract Eclogites are distributed for more than 500 km along a major tectonic boundary between the Sino-Korean and Yangtze cratons in central and eastern China. These eclogites usually have high-P assemblages including omphacite + kyanite and/or coesite (or its pseudomorph), and form a high-P eclogite terrane. They occur as isolated lenses or blocks 10 cm to 300 m long in gneisses (Type I), serpentinized garnet peridotites (Type II) and marbles (Type III). Type I eclogites were formed by prograde metamorphism, and their primary metamorphic mineral assemblage consists mainly of garnet [pyrope (Prp) = 15–40 mol%], omphacite [jadeite (Jd) = 34–64 mol%], pargasitic amphibole, kyanite, phengitic muscovite, zoisite, an SiO2 phase, apatite, rutile and zircon. Type II eclogites characteristically contain no SiO2 phase, and are divided into prograde eclogites and mantle-derived eclogites. The prograde eclogites of Type II are petrographically similar to Type I eclogites. The mantle-derived eclogites have high MgO/(FeO + Fe2O3) and Cr2O3 compositions in bulk rock and minerals, and consist mainly of pyrope-rich garnet (Prp = 48–60 mol%), sodic augite (Jd = 10–27 mol%) and rutile. Type III eclogites have an unusual mineral assemblage of grossular-rich (Grs = 57 mol%) garnet + omphacite (Jd = 30–34 mol%) + pargasite + rutile.Pargasitic and taramitic amphiboles, calcic plagioclase (An68), epidote, zoisite, K-feldspar and paragonite occur as inclusions in garnet and omphacite in the prograde eclogites. This suggests that the prograde eclogites were formed by recrystallization of epidote amphibolite and/or amphibolite facies rocks with near-isothermal compression reflecting crustal thickening during continent–continent collision of late Proterozoic age. Equilibrium conditions of the prograde eclogites range from P 〉 26 kbar and T= 500–750°C in the western part to P 〉 28 kbar and T= 810–880°C in the eastern part of the high-P eclogite terrane. The prograde eclogites in the eastern part are considered to have been derived from a deeper position than those in the western part. Subsequent reactions, manifested by (1) narrow rims of sodic plagioclase or paragonite on kyanite and (2) symplectites between omphacite and quartz are interpreted as an effect of near-isothermal decompression during the retrograde stage. The conditions at which symplectites re-equilibrated tend to increase from west (P 〈 10 kbar and T 〈 580°C) to east (P 〉 9 kbar and T 〉 680°C). Equilibrium temperatures of Type II mantle-derived eclogites and Type III eclogite are 730–750°C and 680°C, respectively.
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  • 80
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract Fluid evolution paths in the COHN system can be calculated for metamorphic rocks if there are relevant data regarding the mineral assemblages present, and regarding the oxidation and nitrodation states throughout the entire P-T loop. The compositions of fluid inclusions observed in granulitic rocks from Rogaland (south-west Norway) are compared with theoretical fluid compositions and molar volumes. The fluid parameters are calculated using a P-T path based on mineral assemblages, which are represented by rocks within the pigeonite-in isograd and by rocks near the orthopyroxene-in isograd surrounding an intrusive anorthosite massif. The oxygen and nitrogen fugacities are assumed to be buffered by the coexisting Fe-Ti oxides and Cr-carlsbergite, respectively. Many features of the natural fluid inclusions, including (1) the occurrence of CO2-N2-rich graphite-absent fluid inclusions near peak M2 metamorphic conditions (927° C and 400 MPa), (2) the non-existence of intermediate ternary CO2-CH4-N2 compositions and (3) the low-molar-volume CO2-rich fluid inclusions (36–42 cm3 mol−1), are reproduced in the calculated fluid system. The observed CO2-CH4-rich inclusions with minor N2 (5 mol%) should also include a large proportion of H2O according to the calculations. The absence of H2O from these natural high-molar-volume CO2-CH4-rich inclusions and the occurrence of natural CH4-N2-rich inclusions are both assumed to result from preferential leakage of H2O. This has been previously experimentally demonstrated for H2O-CO2-rich fluid inclusions, and has also been theoretically predicted. Fluid-deficient conditions may explain the relatively high molar volumes, but cannot be used to explain the occurrence of CH4-N2-rich inclusions and the absence of H2O.
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  • 81
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract Declining temperatures during decay of a hydrothermal system, or during uplift and erosion, tend to result in veins involving progressive hydration reactions, e.g. veins with laumontite cutting prehnitepumpellyite facies rocks, and stilbite veins cutting laumontite veins.In contrast, examples are described of analcime replacement of heulandite along fractures in heulanditized vitric tuff, of replacement of analcime by albite along fractures in quartz-analcime rock, of joint-controlled replacement of heulandite in tuff by laumontite + quartz + (Na, K)-feldspars, of replacement of laumontite by prehnite + quartz along fractures in alumontitized vitric tuff, and of laumontitebearing feldspathic sandstones cut by vein assemblages of quartz and prehnite ° Calcite. The vein mineral assemblage, sometimes with pumpellyite and/or epidote in the prehnite-bearing veins, tends to spread as a zone of dehydration into the adjacent country rock. Except perhaps for albite replacement of analcime, and for laumontite replacement of heulandite, these open-system reactions involve cation activity ratios in the fluid. All involve dehydration. They are favoured by an increase in temperature, and except under certain situations where P-T equilibrium curves have negative slopes, are favoured by a fall in PH2O. Evidence indicates that in at least some cases the triggering mechanism was a drop in PH2O; this may be a widespread phenomenon associated with brittle fracture in the seismogenic upper crust. This may cause fluid pressure to drop from values approaching lithostatic to nearer hydrostatic, and equilibrium may be displaced to yield a less hydrous assemblage that appears as a dehydration vein and vein verge. The dehydration vein assemblage may be diagnostic of a higher grade mineral facies and adds to the mineral complexity attributable to varying permeabilities and fluid pressures in upper crustal strata. Mineral facies are likely to be more uniformly distributed in higher grade rocks from below the brittle-ductile transition zone.Reactions involving complex solid solutions are inappropriate as facies boundaries.
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  • 82
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    Topics: Geosciences
    Notes: Abstract Mg–Fe carpholite is widespread in the Diahot region of New Caledonia in highly aluminous schists and as veins in what was originally a clay-rich hydrothermal alteration envelope about massive suphide deposits. These carpholites have Fe/(Fe + Mg) ratios of 0.03–0.65 and no significant Mn component. Mg-carpholite + quartz occur in assemblages with chlorite or pyrophyllite, pyrophyllite + kaolinite and pyrophyllite + diaspore. Temperatures of 230–320° C and minimum pressures of 7 kbar are indicated for the Mg–Fe carpholite-bearing rocks. The regional distribution of aragonite and Mg–Fe carpholite parallel to a major zone of dominantly transcurrent movement and oblique to the trend of the subduction complex indicates the high-P/low-T schists owe their rapid uplift and preservation to the vertical component of the transcurrent faulting.
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  • 83
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract A metasomatic diopside rock occurs at the top of the dolomitic Connemara Marble Formation of western Ireland and contains titanite and K-feldspar in addition to around 90% diopside (XMg= 0.90–0.97). U–Pb isotopic measurements on this mineral assemblage show that the titanite is both unusually uranium-rich and isotopically concordant, with the result that a precise U–Pb age of 478 ± 2.5 Ma can be determined. The age is identical within error to a less precise Rb–Sr age of diopside–K-feldspar of 483 ± 6 Ma. Petrological evidence indicates that the assemblage crystallized at c. 620° C close to or below the closure temperature of titanite. The age thus provides a precise estimate of the time of metamorphism; this age is 11 ± 3 Ma younger than the 490 Ma age for nearby gabbroic plutons which has previously been used to constrain the peak metamorphic age. This difference accords well with geological evidence that the gabbros were emplaced prior to the metamorphic peak. Analysis of minerals with high closure temperature from assemblages whose crystallization is unambiguously associated with a specific episode of fluid infiltration at the peak of metamorphism provides the basis for a new approach to dating metamorphism. The success of this approach is demonstrated by the results from Connemara.
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  • 84
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract Eclogites with a wide range in bulk composition are present in the Münchberg Massif, part of the Variscan basement of the Bohemian Massif in north-east Bavaria. New analyses of the primary phases garnet, omphacite, phengite and amphibole, as well as the secondary phases clinopyroxene II, various amphiboles, biotite/phlogopite, plagioclase, margarite, paragonite, prehnite and pumpellyite, reveal a complex uplift history. New discoveries were made of samples with very jadeite-rich primary omphacite as well as a secondary omphacite in a symplectite with albite. Various geothermobarometric techniques, together with thermodynamic databases (incorporating separately determined activity–composition values) and experimental data have clustered the minimum conditions for the primary assemblages to the P–T range 650 ± 60° C, 14.3 ± 1 kbar. However, jadeite (in omphacite)–kyanite–paragonite (in phengite) and zoisite–grossular (in garnet)–kyanite–quartz relationships suggests pressures of 25–28 kbar at the same temperatures. The fact that the secondary omphacite–plagioclase assemblage yields pressures within a few hundred bars of the minimum pressures for the plagioclase-free assemblages strongly suggests that the minimum values are serious underestimates.Zoning, inclusion suites and breakdown reactions of primary phases, in addition to new minerals formed during uplift, define a polyphase metamorphic evolution which, from geochronological evidence, occurred solely within the Variscan cycle. The complex breakdown in other Bohemian Massif eclogites and the distinct variation in their temperatures during uplift suggest a multi-stage thrusting model for the regional evolution of the eclogites. Such an evolution has significance with respect to incorporation of mantle slices into crustal sequences and fluid derivation from successively subducted units, possibly driving the breakdown reactions.
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  • 85
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    Journal of metamorphic geology 12 (1994), S. 0 
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    Topics: Geosciences
    Notes: Clay mineral crystallinity and crystallite (domain) size data determined by X-ray diffraction (XRD) are methods extensively used in the characterization of very low-grade metamorphic conditions. However, the lack of sufficient interlaboratory standardization has made comparisons between different research groups unreliable due to significant variations in numerical results obtained, a consequence of the different machine conditions, measurement methods and sample preparations used during analysis. A calibration approach to the standardization of data using rock chip standards is presented, which allows data sets produced by different research groups to be directly and quantitatively compared. A standardized scale, the crystallinity index standard (CIS), is proposed, with illite crystallinity anchizonal boundary limits of 0.25d̀Δ2θ and 0.42d̀Δ2θ, and equivalent illite crystallite sizes of 52 and 23 nm, respectively, determined by the Warren-Averbach method. Calibrating both old and new data will enable more reliable comparisons between similar and contrasting geological environments, and should improve the accuracy and reliability of correlations made between XRD data and other indicators of very low-grade metamorphism, hence increasing the value of such clay mineral studies.
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  • 86
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    Journal of metamorphic geology 12 (1994), S. 0 
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  • 87
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    Journal of metamorphic geology 12 (1994), S. 0 
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    Topics: Geosciences
    Notes: The Chicago mineral-carbonate oxygen isotope fractionation curves have been combined with mineral-water fractionation data for jadeite, zoisite and rutile and new data for grossular-water to provide a set of self-consistent mineral-pair calibrations. The A coefficients in the equation 1000 In α=A× 106T-2 of the new mineral-pair fractionations areJadeite Zoisite Grossular RutileQuartz 1.69 2.00 3.03 5.02Jadeite 0.31 1.34 3.33Zoisite 1.03 3.02Grossular 1.99The isotopic fractionation properties of natural pyralspite garnet [(Ca, Fe, Mg, Mn)3Al2Si3O12] can be approximated by those of the grossular end-member. Appropriate substitutions also yield coefficients for the solid-solution minerals: sodic pyroxene and epidote, e.g. A quartz-sodic pyroxene= 2.75 - 1.06Xjd, A quartz-epidote= 2.00 + 0.75Xpswhere XJd and XPs are the mole fractions of the jadeite and pistacite components, respectively.The new data set is particularly suitable for the geothermometry of metamorphic rocks. δ18O data from minerals of the high-pressure metamorphic rocks of the Sesia Zone of Italy and Cyclades Complex of Greece yield well-constrained mean temperatures of 572 and 478d̀ C, respectively. Type III blueschist metabasalts of the Franciscan Formation of California give mean quartz-garnet temperatures of 354d̀ C.
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  • 88
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    Journal of metamorphic geology 12 (1994), S. 0 
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    Topics: Geosciences
    Notes: Quantitative modelling of oxygen exchange by diffusion during slow cooling has been compared to the observed oxygen isotope distributions from high-grade metamorphic and granitic rocks of the High Himalayan Crystallines, Langtang Valley, central Nepal, in order to investigate the effect of retrograde diffusional exchange on the preservation of high-temperature, oxygen isotope systematics.Modelled fractionations, using water-present diffusion data reported in the literature, predict quartz-mica fractionations to be much larger than those at peak metamorphic and igneous conditions due to low closure temperatures for micas. Quartz-feldspar fractionations may be less than those at peak conditions, and in some samples may even be slightly negative.The observed oxygen isotope fractionations in the metamorphic rocks are small and largely appear to record equilibrations close to peak conditions determined by other methods. Hence these rocks clearly do not conform to predictions of fluid-present diffusional retrograde exchange. It is suggested that their retrograde history was therefore within an anhydrous closed system in which diffusion was slow and hence mineral closure temperatures were high. The granitic rocks record rather larger quartz-biotite fractionations, approaching those predicted by the diffusion modelling. However, quartz-feldspar fractionations are large and hence, although significant retrograde exchange has clearly occurred, simple diffusion alone is not sufficient to explain the observed data and open-system exchange may be required. The presence of fluids during the retrograde history of this part of the section is supported by petrographic evidence.The different retrograde oxygen exchange histories recorded between the regional metamorphic and magmatic regimes of the Langtang section would appear to support the importance of water on the kinetics of such exchange, and suggests that in its absence, diffusional exchange may become insignificant, allowing oxygen isotope thermometry to record meaningful high-temperature data.
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  • 89
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract At Kottavattam, southern Kerala (India), late Proterozoic homogeneous leptynitic garnet–biotite gneisses of granitic composition have been transformed on a decimetric scale into coarse-grained massive charnockite sensu stricto along a set of conjugate fractures transecting the gneissic foliation. Charnockitization post-dates the polyphase deformation, regional high-grade metamorphism and anatexis, and evidently occurred at a late stage of the Pan-African tectonothermal history. Geothermobarometric and fluid inclusion data document textural and chemical equilibration of the gneiss and charnockite assemblages at similar Plith–T conditions (650–700°C, 5–6 kbar) in the presence of carbonic fluids internally buffered by reaction with graphite and opaque mineral phases (XCO2= 0.7–0.6; XH2O= 0.2–0.3; XN2= 0.1; log fO2= -17.5).Mineralogical zonation indicates that charnockitization of the leptynitic gneiss involved first the breakdown of biotite and oxidation of graphite in narrow, outward-migrating transition zones adjacent to the gneiss, followed by the breakdown of garnet and the neoblastesis of hypersthene in the central charnockite zone. Compared to the host gneiss, the charnockite shows higher concentrations of K, Na, Sr, Ba and Zn and lower concentrations of Mg, Fe, Ti, V, Y, Zr and the HREE, with a complementary pattern in the narrow transition zones of biotite breakdown. The Plith–T–XH2O data and chemical zonation patterns indicate charnockitization through subsolidus-dehydration reaction in an open system. Subsequent residence of the carbonic fluids in the charnockite resulted in low-grade alteration causing modification of the syn-charnockitic elemental distribution patterns and the properties of entrapped fluids. We favour an internally controlled process of arrested charnockitization in which, during near-isothermal uplift, the release of carbonic fluids from decrepitating inclusions in the host gneiss into simultaneously developing fracture zones led to a change in the fluid regime from ‘fluid-absent’in the gneiss to ‘fluid-present’in the fracture zones and to the development of an initial fluid-pressure gradient, triggering the dehydration reaction.
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  • 90
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    Journal of metamorphic geology 12 (1994), S. 0 
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    Topics: Geosciences
    Notes: The assemblages chlorite-pumpellyite-lawsonite-albite-quartz, chlorite-lawsonite-quartz-epidote and chlorite-epidote-albite-quartz occur in metabasaltic blocks and veins in a metamorphosed tectonic mélange in the structurally highest unit of the autochthonous and parautochthonous section underlying the Semail ophiolite in Saih Hatat, north-east Oman. The pre-Permian basement of this section contains mafic units characterized by the assemblage crossite-epidote-chlorite-quartz-albite /el actinolite. These assemblages indicate a down-section increase in metamorphic grade from ‘lawsonite-albite facies' conditions in the mélange to ‘epidote-blueschist’ facies conditions in the basement.Application of empirically and experimentally based thermobarometers as well as petrogenetic grids calculated for a model basaltic system indicates that the P-T conditions of metamorphism ranged from 3 to 6 kbar and 250 to 300d̀ C for the mélange and P 〉 6.8 kbar, T 〉 310d̀ C for the basement units. Textural relations interpreted in the context of petrogenetic grids indicate that these units followed clockwise P-T paths of evolution. The estimated P-T conditions and down-section increase in metamorphic grade in central, western and northern Saih Hatat are consistent with the hypothesis relating metamorphism to the Late Cretaceous tectonic loading of the continental margin by an ophiolite slab 〈 18 km in thickness. These results contrast with field and petrological observations documented for blueschists and eclogites exposed along the eastern coast of Saih Hatat which may have formed at an earlier stage in response to an Early Cretaceous collisional event.
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  • 91
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    Journal of metamorphic geology 12 (1994), S. 0 
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  • 92
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    Journal of metamorphic geology 1 (1983), S. 0 
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    Topics: Geosciences
    Notes: The equilibrium thermodynamics of the reaction:And the equilibrium constant is composed of activities formulated using ideal mixing on sites. Consideration is given to the evaluation of uncertainties in pressures calculated using the geobarometer. Preliminary testing suggests that the geobarometer has considerable potential. Much wider testing is now required.
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  • 93
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    Journal of metamorphic geology 1 (1983), S. 0 
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    Topics: Geosciences
    Notes: Abstract. Pink piemontite-spessartine-bearing and grey-green spessartine-bearing manganiferous quartzose schists derived from siliceous pelagites, and green quartzofeldspathic schists, are described from the greenschist facies of the Haast Schist terrane, near Arrow Junction, western Otago. Electron microprobe data are reported for sphene, spessartine-rich garnet, manganoan epidote, piemontite, tourmaline, phengitic muscovite, chlorite, albite, haematite, rutile, manganoan calcite and chalcopyrite.Metamorphism occurred at about 6.4kbar, 400°C. Xco2 was above the quartz-rutile-calcite-sphene buffer (Xco2± 0.02) throughout the recorded metamorphic history of the piemontite schists. It dropped from above to below this critical buffering value in a spessartine-rich schist and it was close to or below the buffering value in the quartzofeldspathic schists. Production of piemontite required high fO2, believed to be inherited from MnOx in the parent pelagite. Substantial loss of O2 (e.g. minimum of 0.19% by weight in one rock) during diagenesis and/or metamorphism is inferred. In the grey-green schists this inhibited piemontite formation. Slight loss of O2 and Ca2+ accompanied minor late-stage replacement of piemontite by second generation spessartine. Observed zoning and mineral replacements indicate rise of temperature, drop in pressure, or invasion by solutions of lower fO2 and XCO2 equilibrated with surrounding schists.The detailed chemistry of the minerals studied correlates with available Mn and with bulk-rock (Fe3+ x 100)/(Fe2++ Fe3+). The oxidation ratio ranges from 24 in average green quartzofeldspathic schist, through 78 in average grey-green manganiferous quartzose schist, to almost 100 in some piemontite-bearing schists. As Fe2+ gives way to Fe3+, Mg/Fe ratios tend to rise in chlorite, phengite, tourmaline, spessartine, and calcite, Mn increases and Ti decreases in haematite, Mn increases in spessartine and calcite, and Fe increases in rutile. Available divalent cations are depleted relative to Al; chlorite is more aluminous, and phengite more paragonitic than in typical Haast schists.
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  • 94
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    Journal of metamorphic geology 11 (1993), S. 0 
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    Topics: Geosciences
    Notes: Abstract Large calcite veins and pods in the Proterozoic Corella Formation of the Mount Isa Inlier provide evidence for kilometre-scale fluid transport during amphibolite facies metamorphism. These 10- to 100-m-scale podiform veins and their surrounding alteration zones have similar oxygen and carbon isotopic ratios throughout the 200 × 10-km Mary Kathleen Fold Belt, despite the isotopic heterogeneity of the surrounding wallrocks. The fluids that formed the pods and veins were not in isotopic equilibrium with the immediately adjacent rocks. The pods have δ13Ccalcite values of –2 to –7% and δ18Ocalcite values of 10.5 to 12.5%. Away from the pods, metadolerite wallrocks have δ18Owhole-rock values of 3.5 to 7%. and unaltered banded calc-silicate and marble wallrocks have δ13Ccalcite of –1.6 to –0.6%, and δ18Ocalcite of 18 to 21%. In the alteration zones adjacent to the pods, the δ18O values of both metadolerite and calc-silicate rocks approach those of the pods. Large calcite pods hosted entirely in calc-silicates show little difference in isotopic composition from pods hosted entirely in metadolerite. Thus, 100- to 500-m-scale isotopic exchange with the surrounding metadolerites and calc-silicates does not explain the observation that the δ18O values of the pods are intermediate between these two rock types. Pods hosted in felsic metavolcanics and metasiltstones are also isotopically indistinguishable from those hosted in the dominant metadolerites and calc-silicates. These data suggest the veins are the product of infiltration of isotopically homogeneous fluids that were not derived from within the Corella Formation at the presently exposed crustal level, although some of the spread in the data may be due to a relatively small contribution from devolatilization reactions in the calc-silicates, or thermal fluctuations attending deformation and metamorphism. The overall L-shaped trend of the data on plots of δ13C vs. δ18O is most consistent with mixing of large volumes of externally derived fluids with small volumes of locally derived fluid produced by devolatilization of calc-silicate rocks. Localization of the vein systems in dilatant sites around metadolerite/calc-silicate boundaries indicates a strong structural control on fluid flow, and the stable isotope data suggest fluid migration must have occurred at scales greater than at least 1 km. The ultimate source for the external fluid is uncertain, but is probably fluid released from crystallizing melts derived from the lower crust or upper mantle. Intrusion of magmas below the exposed crustal level would also explain the high geothermal gradient calculated for the regional metamorphism.
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    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The widespread khondalite series of south-east Inner Mongolia consists largely of biotite–sillimanite–garnet gneiss and quartzo-feldspathic gneiss with some marble and mafic granulite layers. It has experienced two metamorphic events at c. 2500 and 1900–2000 Ma.A pre-peak stage of the first metamorphism at T= 600–700°C and P 〉 6–7 kbar is recognized by the relict amphibolite facies assemblage Ky–Grt–Bt–Pl–Qtz and ‘protected’inclusions of biotite, hornblende, sodic plagioclase and quartz in garnet or orthopyroxene. The peak stage, with T=c. 800 ± 50°C and P 8–10 kbar, is characterized by the widespread granulite facies assemblages Sil–Grt–Bt–Kfs–Pl–Qtz in gneiss and Opx–Cpx–Pl ± Hbl ± Grt in granulite. The P–T–t path suggests that the supracrustal sequence was buried in the lower crust by tectonic thickening during D1–D2.The beginning of the second metamorphism is characterized by further temperature rise to 700°C or more at lower pressure. This stage is manifested by the appearance of cordierite after garnet, fibrolite (Sil2) after biotite in gneiss and transformation of Hbl1 into Opx2 and Cpx2 in granulite. Coronas of symplectitic Opx2 + Pl2 surrounding Grt1 and Cpx1 in mafic granulite are interpreted as products of near-isothermal decompression. The P–T–t path may be related tectonically to waning extension of the crust by the end of the early Proterozoic.
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  • 97
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    Oxford, UK : Blackwell Publishing Ltd
    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The Qinling–Dabie accretionary fold belt in east-central China represents the E–W trending suture zone between the Sino-Korean and Yangtze cratons. A portion of the accretionary complex exposed in northern Hubei Province contains a high-pressure/low-temperature metamorphic sequence progressively metamorphosed from the blueschist through greenschist to epidote–amphibolite/eclogite facies. The ‘Hongan metamorphic belt’can be divided into three metamorphic zones, based on progressive changes in mineral assemblages: Zone I, in the south, is characterized by transitional blueschist–greenschist facies; Zone II is characterized by greenschist facies; Zone III, in the northernmost portion of the belt, is characterized by eclogite and epidote–amphibolite facies sequences. Changes in amphibole compositions from south to north as well as the appearance of increasingly higher pressure mineral assemblages toward the north document differences in metamorphic P–T conditions during formation of this belt. Preliminary P–T estimates for Zone I metamorphism are 5–7 kbar, 350–450°C; estimates for Zone III eclogites are 10–22 kbar, 500 ± 50°C.The petrographic, chemical and structural characteristics of this metamorphic belt indicate its evolution in a northward-dipping subduction zone and subsequent uplift prior to and during the final collision between the Sino-Korean and Yangtze cratons.
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  • 98
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The Lancang metamorphic terrane consists of an eastern low-P/T belt and a western high-P/T belt divided by a N–S-trending fault. Protoliths of both units are mid–late Proterozoic basement and its cover. The low-P/T belt includes the Permian Lincang batholith, related amphibolite facies rocks of the Damenglong and Chongshan groups, and Permo-Triassic volcanic and volcaniclastic rocks. Most whole-rock Rb–Sr isochron and U–Pb zircon ages of the Lincang batholith are in the range 290–279 and 254–212 Ma, respectively. Metamorphism of the low-P/T belt reaches upper amphibolite with local granulite facies (735°C at 5 kbar), subsequently retrogressed at 450–500°C during post-Triassic time. The high-P/T rocks grade from west to east from blueschist through transitional blueschist/greenschist to epidote amphibolite facies. Estimated P–T conditions follow the high-P intermediate facies series up to about 550–600°C, at which oligoclase is stable. The 40Ar/39Ar plateau age of sodic amphibole in blueschist is 279 Ma.The paired metamorphic belts combined with the spatial and temporal distribution of other blueschist belts lead us to propose a tentative tectonic history of south-east Asia since the latest Precambrian. Tectonic juxtaposition of paired belts with contrasting P–T conditions, perhaps during collision of the Baoshan block with south-east Asia, suggests that an intervening oceanic zone existed that has been removed. The Baoshan block is a microcontinent rifted from the northern periphery of Gondwana. Successive collision and amalgamation of microcontinents from either Gondwana or the Panthalassan ocean resulted in rapid southward continental growth of c. 500 km during the last 200 Ma. Hence, the Lancang region in south-east Asia represents a suture zone between two contrasting microcontinents.
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  • 99
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The high-grade metamorphic rocks of southern Brittany underwent a complex tectonic evolution under various P-T conditions (high-P, high-T), related to stacking of nappes during Palaeozoic continentcontinent collision.The east to west thrusting observed in the whole belt is strongly perturbed by vertical movements attributed to the ascent of anatectic granites in the high-T area. The field reconstruction of subvertical, closed elliptical structures in gneisses and migmatites, associated with the subhorizontal, doubly radial pattern of stretching lineation in the mica schists, suggests the existence of an elliptical diapiric body buried at depth beneath the present erosion level.Deformation is associated with a complex P-T evolution partly recorded in aluminous gneisses (kinzigites, e.g. morbihanites). A chronology of successive episodes of mineral growth at different compositions is established by detailed studies of the mineral-microstructure relationships in X-Z sections, using the deformation-partitioning concept (low- and high-strain zones).Several thermometric and barometric calibrations are applied to mineral pairs either in contact or not in contact but in equivalent microstructiiral positions with respect to the deformation history. This methodology provides a continuous microstructural control of P-T variations through time and leads to three P-T-t-d paths constructed from numerous successive P-T estimations. Path 1 is a clockwise retrograde path preserved in low-strain zones, which records general exhumation movements after crustal thickening. Paths 2 and 3 are clockwise prograde/retrograde paths from high-strain zones; they are interpreted and discussed in the light of models of crustal anatexis and upward movement of magma (diapirism). Deformation and P-T effects induced by diapirism can be distinguished from the general deformation-metamorphic history of a belt, and would seem to be produced during a late stage of its history.The present microstructural-petrological approach to defining successive mineral equilibria in relation to progressive deformation steps provides a far more accurate evaluation of the metamorphic evolution than is possible by ‘standard’thermobarometry.
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  • 100
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Journal of metamorphic geology 11 (1993), S. 0 
    ISSN: 1525-1314
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences
    Notes: Abstract The metamorphic history of the Middle to Upper Jurassic volcanic and hypabyssal rocks exposed in the Klamath Mountains and Sierra Nevada of California is related, in part, to the rifting of a volcano-plutonic arc. The Callovian to Kimmeridgian rocks exposed in the region consist of, from north-west to south-east, a back-arc ophiolite, a rifted volcanic arc and a volcanic arc complex. All of these units have been metamorphosed and contain various combinations of the phases chlorite, amphibole, epidote, prehnite and pumpellyite. Projection of coexisting phases onto the composition plane MgO/(MgO + FeO) and Al2O3+ Fe2O3 - 0.75 CaO - Na2O through quartz, water, albite and epidote results in consistent mineralogical compatibilities within each region, but crossing tie-lines between regions. This suggests that the volcanic and hypabyssal rocks from each region have equilibrated under different intensive conditions.The back-arc ophiolite in the north has suffered subseafloor high-T/P hydrothermal metamorphism with geothermal gradients on the order of 100° C km−1. The rifted volcanic arc has undergone synchronous burial, hydrothermal and contact metamorphism. Metamorphic field gradients in the region pass through the prehnite-pumpellyite and greenschist facies suggesting geothermal gradients on the order of 30° C km−1. The southernmost volcanic arc complexes contain metavolcanics of the pumpellyiteactinolite and greenschist facies suggesting moderate- to high-P/T metamorphism and geothermal gradients on the order of 20° C km−1.The apparent increase in rifting and calculated geothermal gradients from south-east to north-west suggest that the observed very low- and low-grade metamorphism may be a response to enhanced thermal gradients during extension of the volcanic arc. This correlation between the extent of rifting and metamorphism is consistent with a model of diastathermal metamorphism of a propagating rift along the western margin of North America during the Late Jurassic. The plate tectonic setting may be analogous to the present-day Andaman Sea region.
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