Resolving diffusion in clay minerals at different time scales: Combination of experimental and modeling approaches

Since no single experimental or modeling technique provides data that allow a description of transport processes in clays and clay minerals at all relevant scales, several complementary approaches have to be combined to understand and explain the interplay between transport relevant phenomena. In this paper molecular dynamics simulations (MD) were used to investigate the mobility of water in the interlayer of montmorillonite (Mt), and to estimate the influence of mineral surfaces and interlayer ions on the water diffusion. Random Walk (RW) simulations based on a simplified representation of pore space in Mt were used to estimate and understand the effect of the arrangement of Mt particles on the meso- to macroscopic diffusivity of water. These theoretical calculations were complemented with quasielastic neutron scattering (QENS) measurements of aqueous diffusion in Mt with two pseudo-layers of water performed at four significantly different energy resolutions (i.e. observation times). The size of the interlayer and the size of Mt particles are two characteristic dimensions which determine the time dependent behavior of water diffusion in Mt. MD simulations show that at very short time scales water dynamics has the characteristic features of an oscillatory motion in the cage formed by neighbors in the first coordination shell. At longer time scales, the interaction of water with the surface determines the water dynamics, and the effect of confinement on the overall water mobility within the interlayer becomes evident. At time scales corresponding to an average water displacement equivalent to the average size of Mt particles, the effects of tortuosity are observed in the meso- to macroscopic pore scale simulations. Consistent with the picture obtained in the simulations, the QENS data can be described using a (local) 3D diffusion at short observation times, whereas at sufficiently long observation times a 2D diffusive motion is clearly observed. The effects of tortuosity measured in macroscopic tracer diffusion experiments are in qualitative agreement with RW simulations. By using experimental data to calibrate molecular and mesoscopic theoretical models, a consistent description of water mobility in clay minerals from the molecular to the macroscopic scale can be achieved. In turn, simulations help in choosing optimal conditions for the experimental measurements and the data interpretation. (C) 2014 Elsevier B.V. All rights reserved.

Reevaluation of the MASTER-2009 MLI and H-10 Debris Modeling

The current paper is an excerpt from the doctoral thesis ”Multi-Layer Insulation as Contribution to Orbital Debris”written at the Institute of Aerospace Systems of the Technische Universit ̈at of Braunschweig. The Multi-Layer In-sulation (MLI) population included in ESA’s MASTER-2009 (M eteoroid and Space-Debris Terrestrial Environment Reference) software is based on models for two mechanisms: One model simulates the release of MLI debris during fragmentation events while another estimates the continuo us release of larger MLI pieces due to aging related deterioration of the material. The aim of the thesis was to revise the MLI models from the base up followed by a re-validation of the simulated MLI debris population. The validation is based on comparison to measurement data of the GEO and GTO debris environment obtained by the Astronomical Institute of the University of Bern (AIUB) using ESA’s Space Debris Telescope (ESASDT), the 1-m Zeiss telescope located at the Optical Ground Station (OGS) at the Teide Observatory at Tenerife, Spain. The re-validation led to the conclusion that MLI may cover a much smaller portion of the observed objects than previously published. Further investigation of the resulting discrepancy revealed that the contribution of altogether nine known Ariane H-10 upper stage explosion events which occurred between 1984 and 2002 has very likely been underestimated in past simulations.

Millennial to orbital-scale variations of drought intensity in the Eastern Mediterranean

Millennial to orbital-scale rainfall changes in the Mediterranean region and corresponding variations in vegetation patterns were the result of large-scale atmospheric reorganizations. In spite of recent efforts to reconstruct this variability using a range of proxy archives, the underlying physical mechanisms have remained elusive. Through the analysis of a new high-resolution sedimentary section from Lake Van (Turkey) along with climate modeling experiments, we identify massive droughts in the Eastern Med- iterranean for the past four glacial cycles, which have a pervasive link with known intervals of enhanced North Atlantic glacial iceberg calving, weaker Atlantic Meridional Overturning Circulation and Dansgaard-Oeschger cold conditions. On orbital timescales, the topographic effect of large Northern Hemisphere ice sheets and periods with minimum insolation seasonality further exacerbated drought intensities by suppressing both summer and winter precipitation.

The position effect in a Rasch-homogenous test: A fixed-links modeling approach.

The position effect describes the influence of just-completed items in a psychological scale on subsequent items. This effect has been repeatedly reported for psychometric reasoning scales and is assumed to reflect implicit learning during testing. One way to identify the position effect is fixed-links modeling. With this approach, two latent variables are derived from the test items. Factor loadings of one latent variable are fixed to 1 for all items to represent ability-related variance. Factor loadings on the second latent variable increase from the first to the last item describing the position effect. Previous studies using fixed-links modeling on the position effect investigated reasoning scales constructed in accordance with classical test theory (e.g., Raven’s Progressive Matrices) but, to the best of our knowledge, no Rasch-scaled tests. These tests, however, meet stronger requirements on item homogeneity. In the present study, therefore, we will analyze data from 239 participants who have completed the Rasch-scaled Viennese Matrices Test (VMT). Applying a fixed-links modeling approach, we will test whether a position effect can be depicted as a latent variable and separated from a latent variable representing basic reasoning ability. The results have implications for the assumption of homogeneity in Rasch-homogeneous tests.

Dark matter sensitivity of multi-ton liquid xenon detectors

We study the sensitivity of multi ton-scale time projection chambers using a liquid xenon target, e.g., the proposed DARWIN instrument, to spin-independent and spin-dependent WIMP-nucleon scattering interactions. Taking into account realistic backgrounds from the detector itself as well as from neutrinos, we examine the impact of exposure, energy threshold, background rejection efficiency and energy resolution on the dark matter sensitivity. With an exposure of 200 t x y and assuming detector parameters which have been already demonstrated experimentally, spin-independent cross sections as low as 2.5×10−49 cm2 can be probed for WIMP masses around 40 GeV/c2. Additional improvements in terms of background rejection and exposure will further increase the sensitivity, while the ultimate WIMP science reach will be limited by neutrinos scattering coherently off the xenon nuclei.

Genetic diversity and differentiation follow secondary succession in a multi-species study on woody plants from subtropical China

Aims: Species diversity and genetic diversity may be affected in parallel by similar environmental drivers. However, genetic diversity may also be affected independently by habitat characteristics. We aim at disentangling relationships between genetic diversity, species diversity and habitat characteristics of woody species in subtropical forest. Methods: We studied 11 dominant tree and shrub species in 27 plots in Gutianshan, China, and assessed their genetic diversity (Ar) and population differentiation (F’ST) with microsatellite markers. We tested if Ar and population specific F’ST were correlated to local species diversity and plot characteristics. Multi-model inference and model averaging were used to determine the relative importance of each predictor. Additionally we tested for isolation-by-distance and isolation-by-elevation by regressing pairwise F’ST against pairwise spatial and elevational distances. Important findings: Genetic diversity was not related to species diversity for any of the study species. Thus, our results do not support joint effects of habitat characteristics on these two levels of biodiversity. Instead, genetic diversity in two understory shrubs, Rhododendron simsii and Vaccinium carlesii, was affected by plot age with decreasing genetic diversity in successionally older plots. Population differentiation increased with plot age in Rhododendron simsii and Lithocarpus glaber. This shows that succession can reduce genetic diversity within, and increase genetic diversity between populations. Furthermore, we found four cases of isolation-by-distance and two cases of isolation-by-elevation. The former indicates inefficient pollen and seed dispersal by animals whereas the latter might be due to phenological asynchronies. These patterns indicate that succession can affect genetic diversity without parallel effects on species diversity and that gene flow in a continuous subtropical forest can be restricted even at a local scale.

Differences in grain growth of calcite: a field-based modeling approach

Normal grain growth of calcite was investigated by combining grain size analysis of calcite across the contact aureole of the Adamello pluton, and grain growth modeling based on a thermal model of the surroundings of the pluton. In an unbiased model system, i.e., location dependent variations in temperature-time path, 2/3 and 1/3 of grain growth occurs during pro- and retrograde metamorphism at all locations, respectively. In contrast to this idealized situation, in the field example three groups can be distinguished, which are characterized by variations in their grain size versus temperature relationships: Group I occurs at low temperatures and the grain size remains constant because nano-scale second phase particles of organic origin inhibit grain growth in the calcite aggregates under these conditions. In the presence of an aqueous fluid, these second phases decay at a temperature of about 350 °C enabling the onset of grain growth in calcite. In the following growth period, fluid-enhanced group II and slower group III growth occurs. For group II a continuous and intense grain size increase with T is typical while the grain growth decreases with T for group III. None of the observed trends correlate with experimentally based grain growth kinetics, probably due to differences between nature and experiment which have not yet been investigated (e.g., porosity, second phases). Therefore, grain growth modeling was used to iteratively improve the correlation between measured and modeled grain sizes by optimizing activation energy (Q), pre-exponential factor (k0) and grain size exponent (n). For n=2, Q of 350 kJ/mol, k0 of 1.7×1021 μmns−1 and Q of 35 kJ/mol, k0 of 2.5×10-5 μmns−1 were obtained for group II and III, respectively. With respect to future work, field-data based grain growth modeling might be a promising tool for investigating the influences of secondary effects like porosity and second phases on grain growth in nature, and to unravel differences between nature and experiment.