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.     

Oceanic fine structure

Abstract

Measurements by free fall instruments, in the San Diego Trough, the Florida Current, and the central Pacific, reveal the detailed structure of the vertical component of the oceanic temperature gradient. The temperature changes are concentrated into regions on the order of a meter thick wherein the measured gradients are often more than ten times the average gradient. The horizontal extent of the regions of high gradient is greater than 750 meters in the seasonal thermocline off San Diego, but is only a few hundred meters at depths greater than 400 meters.

Fine scale measurements show that the layers of high gradient consist of even finer fluctuations in gradient which are only a few centimeters thick. Time scales of the thinnest of these regions of high gradient are of the order of five minutes. The data also yields an estimate of the entropy generation. According to the results of an idealized model relating entropy generation to the turbulent heat transport, only 240 to 700 ergs per cm.² per sec were transported in a 25 meter vertical section measured in the San Diego Trough. This value compared with 3600 ergs per cm.² per sec estimated from the mean gradient and an eddy coefficient of 1 cm.² per sec.     

Groundwater-level response to land-use change and the implications for salinity management in the West Moorabool River catchment, Victoria, Australia

The connection between the removal of native vegetation, rising water tables and increasing stream salinity has been established for many catchments across Australia. However, the West Moorabool River in south west Victoria is an example of a catchment where there has been little discernable effect on groundwater levels following land clearing. Over the past 150 years, a significant portion of the catchment has been cleared of dense forest for agricultural development. Historic standing water-level records from 1870–1871 and 1881 are compared with contemporary measurements (1970s to 2007) recorded in the government bore databases. The data show that the earliest recorded groundwater levels are well within the seasonal range of values observed today. By integrating geology and hydrogeology with historical observations of groundwater levels, climate data and land use, the contemporary field observations of stream salinity are linked to the changed water use and shift in rainfall. In contrast to the normally accepted axiom, reafforestation as a management strategy to mitigate the rising salinity in the West Moorabool River catchment would seem inappropriate.     

A review of numerical experiments on seismic wave scattering

This paper reviews applications of the finite-difference and finite-element methods to the study of seismic wave scattering in both simple and complex velocity models. These numerical simulations have improved our understanding of seismic scattering in portions of the earth where there is significant lateral heterogeneity, such as the crust. The methods propagate complete seismic wavefields through highly complex media and include multiply scattered waves and converted phases (e.g.,P toSV, SV toP, body wave to surface wave). The numerical methods have been especially useful in cases of moderate and strong scattering in complex media where multiple scattering becomes important. Progress has been made with numerical methods in understanding how near-surface, low-velocity basin structures scatter surface waves and vertically-incident body waves. The numerical methods have proven useful in evaluating scattering of surface waves and body waves from topography of both the free surface and interfaces buried at depth. Numerical studies have demonstrated the importance of conversions from body waves to surface waves (andvice versa) when lateral heterogeneities and topographic relief are present in the uppermost crust. Recently, several investigations have applied numerical methods to study seismic wave propagation in velocity models which vary randomly in space. This stochastic approach seeks to understand the effects of small-scale complexity in the earth which cannot be resolved deterministically. These experiments have quantified the relationships between the statistical properties of the random heterogeneity and the measurable properties of high-frequency (1 Hz) seismograms. These simulations have been applied to the study of many features observed in actual high-frequency seismic waves, including: the amplitude and time decay of seismic coda, the apparent attenuation from scattering, the dispersion of waveforms, and the travel time and waveform variations across arrays of receivers.     

Covariance structure and morphometric analysis—A contribution to paleogenetics

A method of analysis of covariance structure proposed by A. P. Dempster complements, in some respects, a recently suggested procedure by the author. The method is based on the comparison of ratios of generalized statistical distances and distancelike quantities. An analysis of septivariate data on the foraminiferTextilina mexicana (Cushman) shows general differences in covariance structure in which the sample rest linear discriminators also differ. This difference in covariance structure is thought to be genetic in origin. Two species of Middle Devonian brachiopods,Martinia inflata (Schnur) andUncites gryphus von Schlotheim), also show differences in covariance structure—the former slightly, the latter strongly. This is further analyzed forUncites by the author's methods and good agreement between the two approaches obtained.     

Detailed measurements during a transient front in a small subtropical estuary

High-resolution measurements of velocity and physio-chemistry were conducted before, during and after the passage of a transient front in a small subtropical system about 2.1 km upstream of the river mouth. Detailed acoustic Doppler velocimetry measurements, conducted continuously at 25 Hz, showed the existence of transverse turbulent shear between 300 s prior to the front passage and 1300 s after. This was associated with an increased level of suspended sediment concentration fluctuations, some transverse shear next to the bed and some surface temperature anomaly.     

A Novel Approach of Using Selected Unconventional Geodesic Methods of Estimation on VTS Areas

Abstract

The Vessel Traffic Service (VTS) systems belong to the fundamental tools used in ensuring a high level of safety across sea basins with heavy traffic, where the presence of navigational hazards poses a great risk of collision or a ship running aground. In order to determine the mutual location of ships, VTS systems obtain information from different facilities, such as coastal radar stations, AIS, and vision systems. Fixing a ship’s position is always accompanied by a degree of error, but the degree of error depends on the specific position fixing system used. In order to increase the accuracy of position fixing in VTS systems, the authors propose the use of contemporary geodetic methods. The article presents the theoretical fundamentals of two unconventional geodesic methods of estimation: M estimation and M_split(q)estimation and the authors’ own proposal of their application in VTS systems. The article concludes with a test verifying theoretical assumptions, performed with the use of a computer application allowing position fixing with the use of selected robust adjustment methods. Furthermore, an example is presented of M_split(q)estimation as used for the acquisition of low-signal radar echoes, which in VTS systems are not automatically identified for tracking. The level of the echo signal makes it difficult for a VTS controller to separate these objects from typical radar noise and interference.