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.     

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     

Environmental history of an urban lake: a palaeolimnological study of Lake Jyväsjärvi, Finland

Sedimentary diatom frustules and chironomid remains, in addition to the chemical stratigraphy of 32 elements and organic pollutants such as resin acids, PCB, DDT and its metabolites, were studied from core samples taken from Lake Jyväsjärvi in Central Finland (64° 14 N, 25° 47 E). The sediment profile covered over 200 years, with the oldest samples representing a period of very low human interference. The town of Jyväskylä was established on the lake shore in 1837, and the lake received untreated municipal wastewater from the town up until, 1977. A paper mill started operations in 1872 and began discharging effluent into Lake Jyväsjärvi. In recent years this effluent loading has been reduced. Based on the biological and chemical properties of the sediment strata, five developmental phases were distinguished and named as follows: (1) a pre-industrial phase (approximately up until the 1860s); (2) a phase of early changes in the lake ecosystem (from the 1870s to ca. 1940s); (3) a phase of increasing eutrophication (from ca. 1950 to ca. 1965); (4) a phase of severe pollution (from ca. 1966 to the early-1990s); and (5) a phase of recovery, which proceeded more quickly during the late-1990s following long-term hypolimnetic aeration. It was estimated that the ecological status of the lake changed from good to moderate during the second phase. Due to the poor chemical status of the lake (including increased concentrations of harmful substances) and the pronounced changes in diatom and chironomid communities, the ecological status from 1950 to the early-1990s was classified as bad. The present ecological status, after a slow recovery of about 20 years, can be classified as moderate/poor. Chemical analysis of the sediment revealed that some elements (C, N, P, S, Ba, Cd, Cu, Fe, Pb, Ni and Zn) followed the known history of municipal waste water discharge into the lake, but Hg, Cr and persistent organic pollutants had different stratigraphies, and therefore mainly originated from other sources. Pronounced changes in profundal benthic communities (chironomids) started about 80 years later than those in diatoms, but later changes in chironomid assemblages were greater than those in diatoms.     

Landscape Controls on Structural Variation in Eucalypt Vegetation Communities: Woronora Plateau,Australia

Quantification of landscape-based vegetation structural variation and pattern is a significant goal for a variety of ecological, monitoring and biodiversity studies. Vegetation structural metrics, derived from airborne laser scanning (ALS or aerial light detection and ranging—LiDAR) and QuickBird satellite imagery, were used to establish the degree of plot-based vegetation variation at a hillslope scale. Topographic position is an indicator of energy and water availability, and was quantified using DEM-based insolation and topographic wetness, respectively, stratifying areas into hot-warm-cold and wet-moist-dry topographic classes. A range of vegetation metrics—maximum and modal canopy height, crown cover, foliage cover, NDVI and semivariance—were compared among randomly selected plots from each topographic class. NDVI increases with increasing landscape wetness, whereas ALS-derived foliage cover decreases with increasing insolation. Foliage cover is well correlated with crown cover (R ² =0.65), and since foliage cover is readily calculable for whole-of-landscape application, it will provide valuable and complementary information to NDVI. Between-plot heterogeneity increases with increasing wetness and decreasing insolation, indicating that more sampling is required in these locations to capture the full range of landscape-based variability. Pattern analysis in landscape ecology is one of the fundamental requirements of landscape ecology, and the methods described here offer statistically significant, quantifiable and repeatable means to realise that goal at a fine spatial grain.     

Chemical signature of intermediate water masses along western Portuguese margin

Although the circulation of intermediate water masses in the eastern North Atlantic remains poorly defined, the presence of fresher intermediate waters, the Sub-Artic (SAIW) and the Antarctic Intermediate Water (AAIW), as well the saline intermediate Mediterranean Water (MW), has been tracked using biogeochemical properties. Here we assess the hydrographic and chemical structures of intermediate waters along the western Portuguese margin by examining the vertical distributions and property-property plots of chemical tracers (oxygen and nutrients). AAIW was traced by low oxygen and high nutrients, while SAIW was recognized by low nutrients. The Mediterranean Water (MW) undercurrent is shown to spread towards the eastern flank of Gorringe bank. Concurrently, the fresher waters gained salt by direct incorporation of MW, while this water was enriched in nutrients on its way northward and westward owing, to a great extent, to the entrainment of an AAIW branch. The distributions of nutrients and apparent oxygen utilization are discussed in terms of regional ocean circulation. Our analysis suggests a circulation pattern of the various intermediate waters along the western Portuguese margin: MW extends all over the area, but its presence is more pronounced around cape St. Vincent; SAIW apparently moves southward, reaching the Gorringe bank region, and AAIW flows northward along the coast and around the bank.