Devitrite (Na2Ca3Si6O16)—structural, spectroscopic and computational investigations on a crystalline impurity phase in industrial soda-lime glasses

Single crystals of devitrite (Na₂Ca₃Si₆O₁₆) were synthesized as pale-yellow transparent needle shaped crystals using a Na₂MoO₄-flux. Experiments aiming to prepare the K-equivalent of devitrite from the corresponding K₂MoO₄-flux were unsuccessful. The crystal structure of devitrite was determined from single-crystal X-ray diffraction data (Mo-K_α radiation, 2θ_max.?=?25.34°, R_int?=?2.66%) and refined in space group P $ \bar{1} $ (no. 2) to R(|F|)?=?3.08% using 2,513 observed reflections with I?>?2σ(I). Unit-cell parameters are: a?=?7.2291(8), b?=?10.1728(12), c?=?10.6727(12) Å, α?=?95.669(9), β?=?109.792(10), γ?=?99.156(9)°, V?=?719.19(14) ų, Z?=?2. The structure belongs to the group of multiple chain silicates consisting of dreier quadruple chains, i.e. the crystallochemical formula can be written as $ {\hbox{N}}{{\hbox{a}}_2}{\hbox{C}}{{\hbox{a}}_3}\left\{ {{\mathbf{uB}}{,4}_\infty^1} \right\}\left[ {^3{\hbox{S}}{{\hbox{i}}_6}} \right.\left. {{{\hbox{O}}_{16}}} \right\} $ . Linkage between the bands running along [100] is provided by double chains of edge sharing CaO₆-octahedra as well as additional more irregularly coordinated Na- and Ca-cations located in the tunnel-like cavities of the mixed tetrahedral-octahedral framework. Structural investigations were completed by Raman and infrared spectroscopical studies. The allocation of the bands to certain vibrational species was aided by density functional theory (DFT) calculations.     

A new perspective on the significance of the Ranotsara shear zone in Madagascar

The Ranotsara shear zone in Madagascar has been considered in previous studies to be a >350-km-long, intracrustal strike-slip shear zone of Precambrian/Cambrian age. Because of its oblique strike to the east and west coast of Madagascar, the Ranotsara shear zone has been correlated with shear zones in southern India and eastern Africa in Gondwana reconstructions. Our assessment using remote sensing data and field-based investigations, however, reveals that what previously has been interpreted as the Ranotsara shear zone is in fact a composite structure with a ductile deflection zone confined to its central segment and prominent NW–SE trending brittle faulting along most of its length. We therefore prefer the more neutral term “Ranotsara Zone”. Lithologies, tectonic foliations, and axial trace trajectories of major folds can be followed from south to north across most of the Ranotsara Zone and show only a marked deflection along its central segment. The ductile deflection zone is interpreted as a result of E–W indentation of the Antananarivo Block into the less rigid, predominantly metasedimentary rocks of the Southwestern Madagascar Block during a late phase of the Neoproterozoic/Cambrian East African Orogeny (c. 550–520 Ma). The Ranotsara Zone shows significant NW–SE striking brittle faulting that reactivates part of the NW–SE striking ductile structures in the flexure zone, but also extends along strike toward the NW and toward the SE. Brittle reactivation of ductile structures along the central segment of the Ranotsara Zone, confirmed by apatite-fission track results, may have led to the formation of a shallow Neogene basin underlying the Ranotsara plain. The present-day drainage pattern suggests on-going normal fault activity along the central segment. The Ranotsara Zone is not a megascale intracrustal strike-slip shear zone that crosscuts the entire basement of southern Madagascar. It can therefore not be used as a piercing point in Gondwana reconstructions.     

Late Pleistocene fluvial dynamics in the Hochrhein Valley and in the Upper Rhine Graben: chronological frame

During the Pleistocene, the Rhine glacier system acted as a major south–north erosion and transport medium from the Swiss Alps into the Upper Rhine Graben, which has been the main sediment sink forming low angle debris fans. Only some aggradation resulted in the formation of terraces. Optically stimulated luminescence (OSL) and radiocarbon dating have been applied to set up a more reliable chronological frame of Late Pleistocene and Holocene fluvial activity in the western Hochrhein Valley and in the southern part of the Upper Rhine Graben. The stratigraphically oldest deposits exposed, a braided-river facies, yielded OSL age estimates ranging from 59.6 ± 6.2 to 33.1 ± 3.0 ka. The data set does not enable to distinguish between a linear age increase triggered by a continuous autocyclical aggradation or two (or more) age clusters, for example around 35 ka and around 55 ka, triggered by climate change, including stadial and interstadial periods (sensu Dansgaard–Oeschger cycles). The braided river facies is discontinuously (hiatus) covered by coarse-grained gravel-rich sediments deposited most likely during a single event or short-time period of major melt water discharge postdating the Last Glacial Maximum. OSL age estimates of fluvial and aeolian sediments from the above coarse-grained sediment layer are between 16.4 ± 0.8 and 10.6 ± 0.5 ka, and make a correlation with the Late Glacial period very likely. The youngest fluvial aggradation period correlates to the beginning of the Little Ice Age, as confirmed by OSL and radiocarbon ages.     

Impacts of tectonic and orbital forcing on East African climate: a comparison based on global climate model simulations

A global atmosphere–ocean model has been forced with topographic and orbital scenarios in order to evaluate the relative role of both factors for the past climate of East Africa. Forcing the model with a significantly reduced topography in Eastern and Southern Africa leads to a distinct increase in moisture transport from the Indian Ocean into the eastern part of the continent and increased precipitation in Eastern Africa. Simulations with step-wise reduced height show that this climate change occurs continuously with the change in topography, i.e., an abrupt change of local climatic features with a critical height is not found. Simulations of the last interglacial (at 125,000 years before present, i.e., the Eemian interglacial) and the last glacial inception (at 115,000 years before present) are used as examples for the role of orbital-induced changes in insolation. Here, changes in meridional temperature gradients lead to modifications in moisture transport of similar order of magnitude, but with different spatial and seasonal structure. For the Eemian interglacial, a distinct increase in summer moisture transport from the Atlantic deep into the continent at around 20°N is simulated.     

A resin nodule in the Cretaceous Garschella Formation from Langer Köchel (Bavaria, S Germany): possible origin and palaeogeographic provenance

A resin nodule was found in glauconite-rich detrital sediments of the Cretaceous Garschella Formation (Aptian to Albian) outcropping at Langer Köchel (Bavaria, S Germany). Gas chromatographic and mass spectrometric analyses of the fossil resin revealed dealkylation and the total defunctionalisation of its polycyclic constituents. Besides many unspecific components a specific one, agathalene, has survived. Agathalene also presents a strongly degraded product, but may have been derived from its natural precursor agathic acid, which is a very specific constituent (biomarker) of recent and fossil kauri resin. Although agathalene is a far less specific secondary biomarker, it indicates the botanic origin of the fossil resin nodule. Besides other potential producers of agathic acid, precursors of the present-day conifer species Agathis dammara and A. australis were distributed in a wider palaeophytogeographic range than today and might have been the botanical source of kauri resin. In view of the east–west directed Early Cretaceous surface current system of the Tethys ocean, the palaeogeographic provenance of the Werdenfels resin nodule probably was a mainland positioned further to the east or southeast of the Helvetic shelf, to where it was transported probably by driftwood of the resin-producing Agathis sp.     

Alpine overdeepenings and paleo-ice flow changes: an integrated geophysical-sedimentological case study from Tyrol (Austria)

We present a study of the inneralpine basin of Hopfgarten focused on the analysis of basin fill in order to reveal its formation in relation to paleo-ice flow and tectonics. The study is based on geological mapping as well as seismic (reflection and refraction) and geoelectrical surveys. The oldest sequence in the basin, identified by seismic stratigraphy at 400 m below surface, consists of coarse grained sediments of supposedly Oligocene to Miocene age, which subsided along faults linked to the Inn fault. Three superimposed sequences, each displaying baselaps in contact with a subglacially formed unconformity and sigmoid foresets, show pleniglacial conditions followed by a glaciolacustrine environment. The uppermost of these three sequences lies on top of last glacial maximum till (LGM; Würmian Pleniglacial; MIS 2) and represents Termination I. The middle sequence is classified as Termination II following the Rissian Pleniglacial (MIS 6). The oldest glacial sequence cannot be constrained chronostratigraphically but might correlate with Termination V following the major glaciation of MIS 12. Limited glacial erosion during the LGM occurred only during the ice build-up phase. Further overdeepening was impeded due to topographic barrier and mutual blockades of glaciers within this highly dissected landscape. The occurrence and relative timing of the impediment was controlled by the onset of transfluences and thus by the altitude of coles. The higher amount of overdeepening during older glacial periods is explained by longer phases of free ice advance in the ice build up phase due to higher transfluences routes at that time. Thus, the preservation of older Pleistocene sequences within the basin may be the result of the lowering of watersheds from one glaciation to the next. Our model of an inverse relationship between glacial shaping of the surface and the subsurface may apply to similar Alpine landscapes as well.     

Spectrometric analyses in comparison to the physiological condition of heavy metal stressed floodplain vegetation in a standardised experiment

Floodplain ecosystems are affected by flood dynamics, nutrient supply as well as anthropogenic activities. Heavy metal pollution poses a serious environmental challenge. Pollution transfer from the soil to vegetation is still present at the central location of Elbe River, Germany. The goal of this study was to assess and separate the current heavy metal contamination of the floodplain ecosystem, using spectrometric field and laboratory measurements. A standardized pot experiment with floodplain vegetation in differently contaminated soils provided the basis for the measurements. The dominant plant types of the floodplains are: Urtica dioica, Phalaris arundinacea and Alopecurus pratensis, these were also chemically analysed. Various vegetation indices and methods were used to estimate the red edge position, to normalise the spectral curve of the vegetation and to investigate the potential of different methods for separating plant stress in floodplain vegetation. The main task was to compare spectral bands during phenological phases to find a method to detect heavy metal stress in plants. A multi-level algorithm for the curve parameterisation was developed. Chemo-analytical and ecophysiological parameters of plants were considered in the results and correlated with spectral data. The results of this study show the influence of heavy metals on the spectral characteristics of the focal plants. The developed method (depth CR1730) showed significant relationship between the plants and the contamination.     

Micro-XCT chondrule classification for subsequent isotope analysis

Chondrules are microscopic, recrystallized melt droplets found in chondritic meteorites. High-resolution isotope analyses of minor elements require large enough element quantities which are obtained by dissolving entire chondrules. This work emphasizes the importance of X-ray computed tomography (XCT) to detect features that can significantly affect the bulk chondrule isotope composition. It thereby expands on other works by looking into chondrules from a wide range of chondrites including CR, CV, CB, CM, L, and EL samples before turning toward complex and time-consuming chemical processing. The features considered are metal and igneous rims, compound chondrules, matrix remnants, and metal contents. In addition to the identification of these features, computed tomography prevents the inclusion of non-chondrule samples (pure matrix or metal) as well as samples where two different chondrule fragments with potentially different isotope compositions are held together by matrix. Matrix surrounding chondrules is also easily detected and the affected chondrules can be omitted or reprocessed. The results strongly encourage to perform XCT before dissolution of chondrules for isotope analysis as a non-invasive method.     

Airborne near-real-time monitoring of assembly and parking areas in case of large-scale public events and natural disasters

A critical requirement for an effective and coordinated response by public entities tasked with management, security, and relief during large-scale public events or natural disasters is the availability of current situational information. However, today there is a lack of comprehensive operational systems allowing a near-real-time (NRT) collection, visualization, and provision of situational information for larger areas. In this study a methodological framework is proposed, which allows an NRT extraction and visualization of situational information based on aerial image acquisition. The framework combines digital image analysis using a generic supervised information extraction approach based on statistical modeling with a downstream web-based visualization component realized through an automatic update of web services. Even though being applicable for different scenarios, the workflow will be demonstrated for the specific use-case of a NRT monitoring of open spaces including assembly and parking areas. Compared to other approaches, image analysis results indicate a high robustness and a low demand for computational power sources (7 seconds per image). Due to a high degree of automation, the proposed workflow contributes to a NRT ‘end-to-end’ monitoring system, which was developed within the VABENE (German acronym for ‘traffic management under large-scale public events and disaster conditions’) project covering all parts from the acquisition of raw aerial imagery to the dissemination of information products to end-users.