A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Granular element method for three‐dimensional discrete element calculations

This paper endows the recently‐proposed granular element method (GEM) with the ability to perform 3D discrete element calculations. By using non‐uniform rational B‐Splines to accurately represent complex grain geometries, we proposed an alternative approach to clustering‐based and polyhedra‐based discrete element methods whereby the need for complicated and ad hoc approaches to construct 3D grain geometries is entirely bypassed. We demonstrate the ability of GEM in capturing arbitrary‐shaped 3D grains with great ease, flexibility, and without excessive geometric information. Furthermore, the applicability of GEM is enhanced by its tight integration with existing non‐uniform rational B‐Splines modeling tools and ability to provide a seamless transition from binary images of real grain shapes (e.g., from 3D X‐ray CT) to modeling and discrete mechanics computations.Copyright © 2013 John Wiley & Sons, Ltd.     

Projected changes in meteorological drought over East Africa inferred from bias-adjusted CMIP6 models

Natural Hazards - The ongoing global warming has caused unprecedented changes in the climate system, leading to an increase in the intensity and frequency of weather and climate extremes. This...     

Development of groundwater favourability map using GIS-based driven data mining models: an approach for effective groundwater resource management

The development of groundwater favourability map is an effective tool for the sustainability management of groundwater resources in typical agricultural regions, such as southern Perak Province, Malaysia. Assessing the potentiality and pollution vulnerability of groundwater is a fundamental phase of favourability mapping. A geographic information system (GIS)-based Boolean operator of a spatial analyst module was applied to combine a groundwater potentiality map (GPM) model and a groundwater vulnerability to pollution index (GVPI) map, thereby establishing the favourable zones for drinking water exploration in the investigated area. The area GPM model was evaluated by applying a GIS-based Dempster–Shafer–evidential belief function model. In the evaluation, six geoelectrically determined groundwater potential conditioning factors (i.e. overburden resistivity, overburden thickness, aquifer resistivity, aquifer thickness, aquifer transmissivity and hydraulic conductivity) were synthesized by employing the probability-based algorithms of the model. The generated thematic maps of the seven hydrogeological parameters of the DRASTIC model were considered as pollution potential conditioning factors and were analysed with the developed ordered weighted average–DRASTIC index model algorithms to construct the GVPI map. Approximately 88.8 and 85.71% prediction accuracies for the Groundwater Potentiality and GVPI maps were established using the reacting operating characteristic curve method and water quality status–vulnerability zone relationship scheme, respectively. Finally, the area groundwater favourability map (GFM) model was produced by applying a GIS-based Boolean operator on the Groundwater Potentiality and GVPI maps. The GFM model reveals three distinct zones: ‘not suitable’, ‘less suitable’ and ‘very suitable’ zones. The area analysis of the GFM model indicates that more than 50% of the study area is covered by the ‘very suitable’ zones. Results produce a suitability map that can be used by local authorities for the exploitation and management of drinking water in the area. The study findings can also be applied as a tool to help increase public awareness of groundwater issues in developing countries.     

Use of fluorescein as a ground water tracer in brackish water aquifers

A drift and pumpback experiment was conducted in a brackish water sandfill. The sandfill was reclaimed from the sea in the eastern part of Singapore and contains sands with low organic and clay/silt contents. The high salinity in the ground water precludes the use of chloride and bromide as tracers in such an environment, and a field experiment was conducted to assess the viability of using fluorescein as a tracer in brackish water aquifers. Nitrate was used as a second tracer to serve as a check. Initial laboratory studies showed that fluorescence was unaffected over the range of electrical conductivity and pH of the ground water. Results from the field experiment show that fluorescein appears to behave conservatively.     

High-resolution subtropical summer precipitation derived from dynamical downscaling of the NCEP/DOE reanalysis: how much small-scale information is added by a regional model?

This study assesses the regional-scale summer precipitation produced by the dynamical downscaling of analyzed large-scale fields. The main goal of this study is to investigate how much the regional model adds smaller scale precipitation information that the large-scale fields do not resolve. The modeling region for this study covers the southeastern United States (Florida, Georgia, Alabama, South Carolina, and North Carolina) where the summer climate is subtropical in nature, with a heavy influence of regional-scale convection. The coarse resolution (2.5° latitude/longitude) large-scale atmospheric variables from the National Center for Environmental Prediction (NCEP)/DOE reanalysis (R2) are downscaled using the NCEP/Environmental Climate Prediction Center regional spectral model (RSM) to produce precipitation at 20?km resolution for 16 summer seasons (1990?C2005). The RSM produces realistic details in the regional summer precipitation at 20?km resolution. Compared to R2, the RSM-produced monthly precipitation shows better agreement with observations. There is a reduced wet bias and a more realistic spatial pattern of the precipitation climatology compared with the interpolated R2 values. The root mean square errors of the monthly R2 precipitation are reduced over 93% (1,697) of all the grid points in the five states (1,821). The temporal correlation also improves over 92% (1,675) of all grid points such that the domain-averaged correlation increases from 0.38 (R2) to 0.55 (RSM). The RSM accurately reproduces the first two observed eigenmodes, compared with the R2 product for which the second mode is not properly reproduced. The spatial patterns for wet versus dry summer years are also successfully simulated in RSM. For shorter time scales, the RSM resolves heavy rainfall events and their frequency better than R2. Correlation and categorical classification (above/near/below average) for the monthly frequency of heavy precipitation days is also significantly improved by the RSM.     

The effect of the wintertime Arctic Oscillation on springtime vegetation over the northern high latitude region

The winter Arctic Oscillation (AO), a major source of climate variability in the Northern Hemisphere, affects winter and the subsequent spring climate over northern high latitude. Such effects are evident even in the 1st eigenmode of the normalized difference vegetation index (NDVI). The impacts of the winter AO is a dipole pattern between Eurasia and North America; positive (negative) values of the winter AO induce warmer (cooler) and high (low) vegetation activity in the following spring over Eurasia (North America). Regarding the time-lagged response of vegetation, the sea surface temperature (SST) and snow cover contribute to maintaining the large-scale circulation anomaly associated with the AO.     

Real Data Assimilation Using the Local Ensemble Transform Kalman Filter (LETKF) System for a Global Non-hydrostatic NWP model on the Cubed-sphere

An ensemble data assimilation system using the 4-dimensional Local Ensemble Transform Kalman Filter is implemented to a global non-hydrostatic Numerical Weather Prediction model on the cubed-sphere. The ensemble data assimilation system is coupled to the Korea Institute of Atmospheric Prediction Systems Package for Observation Processing, for real observation data from diverse resources, including satellites. For computational efficiency in a parallel computing environment, we employ some advanced software engineering techniques in the handling of a large number of files. The ensemble data assimilation system is tested in a semi-operational mode, and its performance is verified using the Integrated Forecast System analysis from the European Centre for Medium-Range Weather Forecasts. It is found that the system can be stabilized effectively by additive inflation to account for sampling errors, especially when radiance satellite data are additionally used.     

Future climate change scenarios over Korea using a multi-nested downscaling system: A pilot study

This study examines a scenario of future summer climate change for the Korean peninsula using a multi-nested regional climate system. The global-scale scenario from the ECHAM5, which has a 200 km grid, was downscaled to a 50 km grid over Asia using the National Centers for Environmental Prediction (NCEP) Regional Spectral Model (RSM). This allowed us to obtain large-scale forcing information for a one-way, double-nested Weather and Research Forecasting (WRF) model that consists of a 12 km grid over Korea and a 3 km grid near Seoul. As a pilot study prior to the multi-year simulation work the years 1995 and 2055 were selected for the present and future summers. This RSM-WRF multi-nested downscaling system was evaluated by examining a downscaled climatology in 1995 with the largescale forcing from the NCEP/Department of Energy (DOE) reanalysis. The changes in monsoonal flows over East Asia and the associated precipitation change scenario over Korea are highlighted. It is found that the RSM-WRF system is capable of reproducing large-scale features associated with the East-Asian summer monsoon (EASM) and its associated hydro-climate when it is nested by the NCEP/DOE reanalysis. The ECHAM5-based downscaled climate for the present (1995) summer is found to suffer from a weakening of the low-level jet and sub-tropical high when compared the reanalysis-based climate. Predicted changes in summer monsoon circulations between 1995 and 2055 include a strengthened subtropical high and an intensified mid-level trough. The resulting projected summer precipitation is doubled over much of South Korea, accompanied by a pronounced surface warming with a maximum of about 2 K. It is suggested that downscaling strategy of this study, with its cloud-resolving scale, makes it suitable for providing high-resolution meteorological data with which to derive hydrology or air pollution models.     

ULYSSES observations of energetic particle acceleration and the superposed CME and CIR events of November 1992

During November 1992, a series of forward and reverse shocks passed the ULYSSES spacecraft. Spectral and anisotropy measurements are reported for protons and alpha particles between 0.28 and 6 MeV observed by the Energetic Particle Composition Experiment, data recorded by the Magnetometer Experiment and the high-energy (2.7-300 MeV) proton data from the Kiel Electron Telescope. An analysis of energetic particle, plasma and magnetometer data from ULYSSES has allowed a unique study of the corresponding arrival of fare particles, particles within a corotating interaction region and particles transported with a coronal mass ejection. We present an analysis of these data in terms of possible diffusive shock acceleration but conclude that this is likely to be incompatible with the short transit time of the particles. Shock drift acceleration of particles with energies 0.3 MeV/nucleon or solar acceleration followed by particle trapping behind the shock front are alternative possibilities.