The use of acidimetric titration as a novel approach to study particulate trace metal speciation and mobility: Application to sediments of the Scheldt estuary

The study of trace metal speciation has benefited from a great deal of interest leading to the development and the diversification of sequential extraction schemes (SES), which triggered the need for harmonization by the standard, measurements and testing programme (SM & T). However, some uncertainties still persist in the application of the harmonized 3-step protocol, because of the difficulty in conceptualizing a technique that can be applied to environmental samples irrespective of their nature. The alternative method proposed in this study is based on the solubility of the sample components progressively dissolved during the course of an acidimetric titration by 1 mol L⁻¹ HCl. The major HCl-reactive mineralogical components are identified using mass balance calculation of H⁺ consumed by their dissolution together with the amount of major elements released into solution. The speciation of minor and trace elements is investigated by comparing their titrations to those of the major elements. This approach is much simpler than SES because it uses simple non-selective H⁺ at room temperature instead of a complex experimental design of so-called specific reagents. The different mineral components of the solid are no longer operationally defined and the problem of selectivity is irrelevant to the titration approach. The method was applied to several sediment samples from the Scheldt estuary and the particulate phase was further examined by Scanning Electron Microprobe and X-ray Diffraction techniques. The nearly complete consumption of H⁺ in the suspension is balanced by the total dissolution of carbonates and Fe-oxyhydroxides. In contrast to the speciation inferred from the Tessier SES, the acidimetric titration has demonstrated that the carbonate phase does not significantly contain trace metals with the exceptions of 40% of the Mn and 30% of the Co. In contrast, the Fe-oxyhydroxides seem to play a major role and account for 70% of Pb and 20% of Cr, in addition to 60% of P and additional amounts of 20% Co and 40% Mn. 70% of the Cu also occur in the oxyhydroxide phase, more likely coprecipitated with gibbsite. 90% of the Cd and 85% of Zn can be attributed to the Acid Volatile Sulfide (AVS) phase as evidenced from S titration. The acidimetric titration method not only provides information on the speciation of trace metals but also allows the quantification of their reactivity and mobility, if one considers that the titration roughly mimics pH changes that may occur as a result of chemical disequilibrium in the environment. The results demonstrate the potential of the acidimetric titration as an alternative to SES protocols in geochemical and environmental regulation studies. This method is applicable to a wide variety of environmental materials with little or minor adjustments.     

VERTICAL SEISMIC PROFILING IN COAL*

The intellection of seismic wave propagation in coal measures demands direct observation of the wavefield progression. Two vertical seismic profiles with high spatial and temporal sampling, were recently recorded in the Sydney Basin coalfields as part of an experimental coal seismic program. Static corrections and interval velocities were obtained by an automated system to determine first kicks and pulse rise times. Upgoing and downgoing waves were separated in the f—k-plane using a novel technique of contour slice filtering. The isolated upgoing waves clearly display reflections from the major coal seams within the stratigraphic sequence. The downgoing wave spectra were subjected to attenuation analysis. The deduced specific quality factor Q for Permian coal measure rocks lies in the range 20–70. Similar estimates were obtained in the time domain from measurements of pulse broadening. Synthetic VSP seismograms, computed using an exact recursive formulation, are an indispensable aid to interpretation. They illustrate the filtering effects of coal seams and sequences, and the effects of the contribution of internal and free-surface multiple reflections in the recorded wavetrains.     

Manganese concentration in the silts of the Mozhaisk Reservoir

The causes of the high Mn concentration in the solid phase and pore solution of bottom sediments in the Mozhaisk Reservoir are discussed. Regularities are identified in variations the concentrations of Mn forms in reservoir deposits from its upper part to the dam.     

Models of travel demand with endogenous preference change and heterogeneous agents

In the literatures of regional science, urban economics, and urban development planning, a working assumption is that individuals respond to incentives and regulations, given their preferences. Models for planning and policy analyses are used to consider what might occur if the incentives or regulations were different. In these models, however, preferences are usually assumed to be given and stable, and agents are usually assumed to be homogeneous. This paper focuses on the implications of making preferences in models of policy implementation endogenously determined and time varying heterogeneous agents. We consider first the recent literature on intertemporal choice and preference change, which cuts across many disciplines, and more briefly the literature on norm-regarding behavior. We then elaborate a simple model of transportation demand—from a static to a dynamic orientation, from fixed and exogenously given preferences of strictly self-regarding agents to endogenously determined and policy-induced preferences of heterogeneous agents—and illustrate its characteristics with simple numerical examples.     

The Role of the Magnetic Field in the Ascension of the 22nd and 23rd Cycles of Activity

The first small active regions of the last two new cycles seem to be formed, in its very first, preparatory stage, close to the equator with uncertain magnetic orientation, and as secondary products at the periphery of equatorial `magnetic bubbles' of the new magnetic flux still belonging to the old cycle. At the real beginning of the new cycle, at the periphery of its higher-latitude `magnetic bubbles', the opposite applies to the secondary regions of the ending cycle. It seems that two modes of magnetic flux supply the visible layers of the photosphere during the cycle transition phase: the emergence of the magnetic flux from the depth of the convective zone, and the mutual interaction of the earlier emerging fluxes, or the action of the `local dynamo', giving rise to the new local magnetic field concentrations.     

Seismic response of light internal equipment in base-isolated structures

The seismic response of light secondary systems in a building is dependent on the response of the primary structural system to the seismic ground motion with the result that very high accelerations can be induced in such secondary systems. This response can be reduced through the use of aseismic base isolation which is a design strategy whereby the entire building can be decoupled from the damaging horizontal components of seismic ground motion by the use of some form of isolation system. The paper presents a theoretical analysis of the response of light equipment in isolated structures and a parallel experimental programme both of which show that the use of base isolation can not only attenuate the response of the primary structural system but also reduce the response of secondary systems. Thus, the design of equipment and piping in a base-isolated building is very much simpler than that for a conventionally founded structure: inelastic response and equipment-structure interaction need not be considered and multiple support response analysis is rendered unnecessary. Although an isolation system with linear elastic bearings can reduce the acceleration of the structure, it may be accompanied by large relative displacements between the structure and the ground. A system using lead-rubber hysteretic bearings, having a force-displacement relation which is approximately a bilinear loop, can reduce these displacements. A parallel experimental programme was carried out to investigate the response of light equipment in structures isolated using lead-rubber bearings. The experimental results show that these bearings can dissipate energy and limit the displacement and acceleration of the structure but are less effective in reducing the accelerations in the internal equipment. The results of both the analysis and the tests show that base isolation is a very effective method for the seismic protection of light equipment items in buildings.     

Existence of transverse waves in anisotropic poroelastic media

Out of the four waves in an anisotropic poroelastic medium, two are termed as quasi-transverse waves. The prefix 'quasi' refers to their polarizations being nearly, but not exactly, perpendicular to direction of propagation. In this composite medium, unlike perfectly elastic medium, the propagation of a longitudinal wave along a phase direction may not be accompanied by transverse waves. The existence of a transverse wave in anisotropic poroelastic media is ensured by the two equations restricting the choice of elastic coefficients of porous aggregate as well as fluid–solid coupling. Necessary and sufficient conditions for the existence of transverse waves along the coordinate axes and in the coordinate planes for general anisotropy are discussed. The discussion is extended to the case of orthotropic materials and existence for few specific phase directions is also explored. The conditions for the transverse waves decided on the basis of their apparent polarizations, that is, particle motion being perpendicular to ray direction, are also discussed. For a particular numerical model, the existence of these apparent transverse waves is solved numerically for phase directions in coordinate planes. For general directions of phase propagation, the existence of these transverse waves is checked graphically for the chosen numerical model.