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.     

Saturn's electrostatic discharges: Could lightning be the cause?

It is proposed that Saturn's electrostatic discharges (SED) might be generated in the planet's equatorial atmosphere, perhaps as lightning from a storm system. The 10^h10^m periodicity of the signal envelope duplicates that of Saturn's equatorial jet. The rings shield the atmosphere from solar EUV photons, and thereby substantially reduce the local ionospheric cutoff frequency to allow low-frequency SED to leak out. Many of the unusual properties of SED could be explained in terms of changes in the storm system, the relative spacecraft position in the beaming pattern of the source, local refraction of the signal by the highly disturbed ionosphere, and the influence of the ring particles on the highest frequency component of SED. A comparison of SED with planetary lightning on other planets shows that the two are similar in general character and some time behavior; the power output of SED may be higher than most planetary lightnings but that is unclear because of uncertainties in the measurements and variations in the signal's spectrum. Our simple discussion suggests that lightning could be a viable source for SED and that exotic ring mechanisms are not necessarily required.     

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.     

Biosorption of Rare-Earth Elements and Yttrium by Heterotrophic Bacteria in an Aqueous Environment

This paper reports the results of the experimental determination of the coefficient of sorption of rare-earth elements and yttrium (REY) under conditions of acidic pH using several strains of heterotrophic bacteria (Microbacterium sp., Curtobacterium sp., Bacillus subtilis, Pseudomonas putida, and Bacillus pumilis) that are widespread in natural and technogenic waters of the Far East (Russia). Insignificant fractionation between heavy and light rare-earth elements, negative cerium and dysprosium anomalies, and a positive europium anomaly were revealed. The selectivity of REY biosorption by gram-positive and gram-negative bacteria, as well as inertia of the biosorption process under more acidic conditions of the medium, were shown.