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.     

The mineralogical composition of precursor sediments of calcareous rhythmites: a new approach

Previous studies in Silurian carbonates from Gotland (Sweden) have led to a model for the development of limestone-marl alternations. This model postulates that early diagenesis of precursor sediments without strong primary differences can result in a differentiation by selective dissolution of aragonite in marl beds and reprecipitation of calcite cement in limestone beds. This model is described as a set of mathematical equations that quantify the diagenetic processes (aragonite dissolution and calcite reprecipitation) that occur during the formation of limestone-marl interbeds from a hypothetical homogeneous precursor sediment. The calculations demonstrate that resulting hypothetical limestone-marl alternations show characteristic mathematical relationships between the ratios of the bed thicknesses of limestones and marls on one side, and the carbonate contents, on the other. By reversing this model, the original mineralogical composition of the precursor sediment of real-world rhythmic successions can be determined. In this study, alternations from the Silurian of Gotland, the Cambrian, Devonian, and Mississippian of North America, the Jurassic of France and Germany, and the Cretaceous of France are shown to exhibit mathematical relationships similar to those calculated for hypothetical precursor sediments without primary differences. Therefore, the mineralogical composition of their precursor sediments can be estimated. In contrast, the clear mismatch shown by the Lower Jurassic Belemnite Marls from Dorset indicates that these rhythms did not suffer an early diagenetic overprint. Our model helps to differentiate between rhythmites with strong depositional variations and those without; however, it cannot indicate whether a given alternation is the product of rhythmic diagenesis of a homogeneous precursor sediment or the result of diagenetic enhancement of subtle underlying sedimentary rhythms. For horizontally correlated patterns, such as laterally extensive beds and layers of nodules, an a priori unknown external signal has to be assumed.     

Performance of small-scale irrigation schemes in Lake Tana Basin of Ethiopia: technical and socio-political attributes

This study was conducted to investigate technical and socio-political attributes that lead to the underperformance of two selected irrigation schemes (Shina and Bebeks) in the Lake Tana floodplains, Ethiopia. Irrigation application efficiency (AE) at nine experimental fields showed a wide range, from 20 to 80%, but was mostly between 40 and 60%. Irrigation water-use efficiency (IWUE) varied from 1.9 to 7.2 kg m^?3 for onion and 0.9 to 1.2 kg m^?3 for maize. The lined and earthen canal conveyance losses in Bebeks were 0.037 and 0.047 l s^?1 m^?1, whereas in Shina they were 0.033 and 0.044 l s^?1 m^?1, respectively. The overall consumed ratio (OCR) of water was 0.58 for Bebeks and varied from 0.73 to 1.2 in Shina. Both schemes are performing below the standard based on technical performance indicators. Irrigation water user associations (WUAs) were not implemented, but irrigation committees (ICs), composed of local political leaders, are managing both schemes. Canal and reservoir sedimentation from erosion of upstream catchment areas during the rainy season was the major problem.     

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.     

PROBLEMS IN CONSTRUCTING A BATHYMETRIC BASE MAP FOR THE GULF OF FINLAND

The various steps required for compilation of a bathymetric chart of the Gulf of Finland are outlined, taking into account the specific conditions characteristic of that water body. The use of available initial source materials and special survey work required for supplementing these sources is discussed. Translated by Edward Torrey, Alexandria, VA 22308 from: Geodeziya i kartografiya, 1988, No. 8, pp. 40-42.     

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.