Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.     

Suction-controlled experiments on Boom clay

The understanding of the thermo-hydro-mechanical behaviour of a clay barrier is needed for the prediction of its final in situ properties after the hydration and thermal transient in a radioactive waste repository.

As part of the CEC 1990–1994 R&D programme on radioactive waste management and storage, the CEA (Fr), CIEMAT (Sp), ENRESA (Sp), SCK · CEN (B), UPC (Sp) and UWCC (UK) have carried out a joint project on unsaturated clay behaviour (Volckaert et al., 1996). The aim of the study is to analyse and model the behaviour of a clay-based engineered barrier during its hydration phase under real repository conditions. The hydro-mechanical and thermo-hydraulic models developed in this project have been coupled to describe stress/strain behaviour, moisture migration and heat transfer. A thermo-hydraulic model has also been coupled to a geochemical code to describe the migration and formation of chemical species.

In this project, suction-controlled experiments have been performed on Boom clay (B), FoCa clay (Fr) and Almeria bentonite (Sp). The aim of these experiments is to test the validity of the interpretive model developed by Alonso and Gens (Alonso et al., 1990), and to build a database of unsaturated clay thermo-hydro-mechanical parameters. Such a database can then be used for validation exercises in which in situ experiments are simulated.

The Boom clay is a moderately swelling clay of Rupellian age. It is studied at the SCK · CEN in Belgium as a potential host rock for a radioactive waste repository. In this paper, suction-controlled experiments carried out on Boom clay by SCK · CEN are described. SCK · CEN has performed experiments to measure the relation between suction, water content and temperature and the relation between suction, stress and deformation. The applied suction-control techniques and experimental setups are detailed. The results of these experiments are discussed in the perspective of the model of Alonso and Gens. The influence of temperature on water uptake was rather small. The measured swelling-collapse behaviour can be explained by the Alonso and Gens model.     

Carbonatation processes at the El Berrocal natural analogue granitic system (Spain): inferences from mineralogical and stable isotope studies

The El Berrocal granite/U-bearing quartz vein system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective is to understand the geochemical behaviour of natural radionuclides occurring under natural conditions. In this framework, the carbonatation processes have been studied from a mineralogical and isotopic ( and ) point of view, since carbonate anions are powerful complexing agents for U(VI) under both low-temperature hydrothermal and environmental conditions. The carbonatation processes in the system are identified by the presence of secondary ankerite, with minor calcite, scattered in the hydrothermally altered granite, and Mn calcite in fracture filling materials. The isotopic signatures of these carbonates lead us to conclude that ankerite and calcite from the former were formed at the end of the same hydrothermal process that altered the granite, at a temperature range of between 72° and 61°C for ankerite, and between 52° and 35°C for calcite. The effect of edaphic CO₂ on both carbonates, greater on calcite than on ankerite, is demonstrated. Calcites from fracture fillings are, at least, binary mixtures, in different proportions, of hydrothermal calcite, formed between 25° and <100°C, and supergenic calcite, formed at ≤25°C. According to their signatures, the effect of edaphic CO₂ in both calcites is also evident. It is assumed that: (i) hydrothermal calcite from fracture fillings and ankerite from the hydrothermally altered granite are the result of the same hydrothermal process, their chemical differences being due to the intensity of the water/rock interaction which was stronger in the altered granite than in the fractures; and (ii) all of these carbonatation processes are responsible for ancient and recent migration/retention of uranium observed in the hydrothermally altered granite and fracture fillings.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

A seismic source zone model for the seismic hazard assessment of the Italian territory

We designed a new seismic source model for Italy to be used as an input for country-wide probabilistic seismic hazard assessment (PSHA) in the frame of the compilation of a new national reference map.

We started off by reviewing existing models available for Italy and for other European countries, then discussed the main open issues in the current practice of seismogenic zoning.

The new model, termed ZS9, is largely based on data collected in the past 10 years, including historical earthquakes and instrumental seismicity, active faults and their seismogenic potential, and seismotectonic evidence from recent earthquakes. This information allowed us to propose new interpretations for poorly understood areas where the new data are in conflict with assumptions made in designing the previous and widely used model ZS4.

ZS9 is made out of 36 zones where earthquakes with M_w > = 5 are expected. It also assumes that earthquakes with M_w up to 5 may occur anywhere outside the seismogenic zones, although the associated probability is rather low. Special care was taken to ensure that each zone sampled a large enough number of earthquakes so that we could compute reliable earthquake production rates.

Although it was drawn following criteria that are standard practice in PSHA, ZS9 is also innovative in that every zone is characterised also by its mean seismogenic depth (the depth of the crustal volume that will presumably release future earthquakes) and predominant focal mechanism (their most likely rupture mechanism). These properties were determined using instrumental data, and only in a limited number of cases we resorted to geologic constraints and expert judgment to cope with lack of data or conflicting indications. These attributes allow ZS9 to be used with more accurate regionalized depth-dependent attenuation relations, and are ultimately expected to increase significantly the reliability of seismic hazard estimates.     

Revisiting Peruvian anchovy (Engraulis ringens) trophodynamics provides a new vision of the Humboldt Current system

The Peruvian anchovy or anchoveta (Engraulis ringens) forages on plankton and is a main prey for marine mammals, seabirds, fish, and fishers, and is therefore a key element of the food web in the Humboldt Current system (HCS). Here, we present results from the analysis of 21,203 anchoveta stomach contents sampled during 23 acoustic surveys over the period 1996–2003. Prey items were identified to the genus level, and the relative dietary importance of different prey was assessed by determination of their carbon content. Variability in stomach fullness was examined relative to the diel cycle, the distance from the coast, sea surface temperature, and latitude, using generalized additive models (GAMs). Whereas phytoplankton largely dominated anchoveta diets in terms of numerical abundance and comprised >99% of ingested prey items, the carbon content of prey items indicated that zooplankton was by far the most important dietary component, with euphausiids contributing 67.5% of dietary carbon followed by copepods (26.3%). Stomach fullness data showed that anchoveta feed mainly during daytime between 07h00 and 18h00, although night-time feeding also made a substantial contribution to total food consumption. Stomach fullness also varied with latitude, distance from the coast, and temperature, but with substantial variability indicating a high degree of plasticity in anchoveta feeding behaviour. The results suggest an ecological role for anchoveta that challenges current understanding of its position in the foodweb, the functioning of the HCS, and trophic models of the HCS.     

Seabed Morphology and Pollution Along the Bagnoli Coast (Naples, Italy): a Hypothesis for Environmental Restoration

Abstract. The interaction of coastal and submarine morphology with the hydrodynamic regimes exerts a control on coastal dynamic processes, conditioning the dispersion of sediments and potential pollutants existing in the area. Thus, the study of such parameters is useful in order to define environmental threats. Within the submerged sector of the Bagnoli coast and particularly in the southern part of the investigated area, there are sediment groups composed of very fine sands located in low-energy zones due to wave refraction and diffraction; they can also be found on the sea bottom and on the man-made structures typical of this zone. These areas show high pollutant levels of N, P, Cu, Fe, Mn, Ni, Pb, Zn, Cd, polyaromatic hydrocarbons (PAHs) and polychlorinated bi-phenyls (PCBs). The northern area, a place of high-energy hydrodynamic processes, also shows high concentration levels of pollutants due to the presence of secondary cell circulation.
Morphological research and analysis of textural characteristics of bottom sediments along the Bagnoli coast allowed the actual processes and their evolution in space and time to be defined. It has also been possible to correlate such processes to the seabed morphology system, the wave formations which affect the coast, the complex system of sediment transport, as well as to the man-made interventions in the area. The results of recent chemical analyses of beach sediments and bottom sediments off the Bagnoli coast were also incorporated. They prove the presence of heavy metals, PAHs and PCBs in high and sometimes very high concentrations. Finally, based on the results of research and analyses, a hypothesis for an intervention for environmental restoration has been formulated in order to renaturalise the coast through dredging and treatment of the sand, both on the seabed and on the emerged beach.     

Seismic vulnerability of bridges in transport networks subjected to environmental deterioration

This paper investigates the problem of management, maintenance and planning of interventions in transport networks located in seismic zones, in relation to the actual state of degradation of their most vulnerable elements, as bridges. The study consists in two phases: the first phase is concerned with definition of the seismic vulnerability of a typical bridge in the network, through the construction of fragility curves calculated taking into account the corrosion of the reinforcing steel as the main cause of environmental deterioration. Once the fragility curves of the deteriorated bridges are computed, the second phase consists in the analysis of the vulnerability of the transport network in which the bridges are included taking into account the modification of the traffic flows when bridge infrastructures are damaged. The results of this pilot study can be used as a first step for a proper allocation of economic resources in the planning of seismic retrofit interventions to minimize the overall risk and manage the immediate post-earthquake emergency phase and guide rescuers in reaching the affected and critical areas.