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.     

Experimental determination of the reaction dolomite + 2 coesite = diopside + 2 CO2 to 6 GPa

 The carbonation reaction CaMg(CO₃)₂ (dolomite)+2SiO₂ (coesite)=CaMgSi₂O₆ (diopside)+2 CO₂ (vapor) has been determined experimentally between 3.5 and 6 GPa in a multiple-anvil, solid-media apparatus. This reaction, a candidate for carbonation of eclogites (garnet+clinopyroxene) in the Earth’s mantle, lies at higher pressure for a given temperature than do the carbonation reactions for peridotites (olivine+orthopyroxene±clinopyroxene). A depth interval may exist within the Earth’s mantle under either ‘normal’ or ‘subduction’ thermal regimes where carbonated peridotite could coexist with carbonate-free, CO₂-bearing eclogite. Received: 25 May 1994/Accepted: 13 June 1995     

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.     

Impact of Earth radiation pressure on GPS position estimates

GPS satellite orbits available from the International GNSS Service (IGS) show a consistent radial bias of up to several cm and a particular pattern in the Satellite Laser Ranging (SLR) residuals, which are suggested to be related to radiation pressure mismodeling. In addition, orbit-related frequencies were identified in geodetic time series such as apparent geocenter motion and station displacements derived from GPS tracking data. A potential solution to these discrepancies is the inclusion of Earth radiation pressure (visible and infrared) modeling in the orbit determination process. This is currently not yet considered by all analysis centers contributing to the IGS final orbits. The acceleration, accounting for Earth radiation and satellite models, is introduced in this paper in the computation of a global GPS network (around 200 IGS sites) adopting the analysis strategies from the Center for Orbit Determination in Europe (CODE). Two solutions covering 9 years (2000–2008) with and without Earth radiation pressure were computed and form the basis for this study. In previous studies, it has been shown that Earth radiation pressure has a non-negligible effect on the GPS orbits, mainly in the radial component. In this paper, the effect on the along-track and cross-track components is studied in more detail. Also in this paper, it is shown that Earth radiation pressure leads to a change in the estimates of GPS ground station positions, which is systematic over large regions of the Earth. This observed “deformation” of the Earth is towards North–South and with large scale patterns that repeat six times per GPS draconitic year (350 days), reaching a magnitude of up to 1 mm. The impact of Earth radiation pressure on the geocenter and length of day estimates was also investigated, but the effect is found to be less significant as compared to the orbits and position estimates.