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.     

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.     

Marine risk assessment: linear alkylbenzenesulponates (LAS) in the North Sea

The fate of linear alkylbenzenesulponates (LAS) in estuaries and coastal areas of the North Sea has been characterized with simple environmental models. The predicted concentration range in the estuaries around the North Sea (0.9-9 microg LAS l(-1)) was validated by monitoring data (1-9 microg LAS l(-1)). In offshore sites of the North Sea, it is estimated--and experimentally verified for a few sites--that the LAS concentration is below analytical detection limit (i.e., 0.5 microg LAS l(-1)). The effects of LAS on marine organisms have been reviewed. For short-term acute tests, there was no significant difference (p = 0.83) between the mean LC50 values of freshwater and marine organisms (mainly pelagic species tested, 4.1 and 4.3 mg LAS l(-1), respectively). For longer-term chronic tests, it appeared that the sensitivity (mean no-observed effect concentration (NOEC) value) of marine and freshwater organisms (0.3 and 2.3 mg LAS l(-1), respectively) was significantly different pt-test = 0.007). The predicted no-effect-concentrations (PNEC) were 360 and 31 microg LAS l(-1), for freshwater and marine pelagic communities, respectively. Given that the maximum expected estuarine and marine concentrations are 3 to > 30 times lower than the PNEC, the risk of LAS to pelagic organisms in these environments is judged to be low.     

CLIMAP SSTs re-revisited

Since the 1976 publication of the CLIMAP ice age sea surface temperature (SST) reconstruction showing a 1–2 ^∘C tropical cooling a substantial debate has arisen as to whether tropical SSTs may instead have been 4–5^∘ colder than present. Herein I review the arguments for large SST variations and question a number of key findings, particularly the validity of ice-age coral SST estimates and “down-projecting” tropical snowline changes to the surface. GCM results indicate that an intermediate solution requiring ∼2.5 ^∘C warm pool cooling is consistent with most quantitative low elevation surface land data and is small enough to allow the persistence of tropical biota in the ocean during glacial times. The proposal reduces estimated ice-age climate sensitivity (for a doubling of CO₂) from a “high-end” sensitivity of about 4.5 ^∘C (for a 5–6 ^∘C tropical cooling) to a “mid-range” sensitivity of about 3.0 ^∘C for a 2.5 ^∘C warm-pool decrease. Received: 28 July 1999 /Accepted: 12 August 1999     

Thermonuclear burning ignition and propagation in surface layers of neutron stars. 1. General study and one-zone model without mass-flow

We develop and study a general model describing ignition and propagation of burning. It is applied to explosive thermonuclear burning in surface layers of neutron stars. For this purpose an one-zone model of a thin surface layer is developed. We study thermonuclear burning ignition and propagation along the layer with its help.