Modelling the long-term dynamics of radiocaesium in closed lakes

During the years after the Chernobyl accident the radioceasium activity concentration in most contaminated aquatic ecosystems decreased markedly. Lakes with no permanent inflows and outflows (closed lakes), however, still present a radioecological problem which is expected to continue for some time. In this paper, a mechanistic model for the long-term prediction of radiocaesium behaviour in closed lakes is developed. The model of Prokhorov (Radiokhimiya (Radiochemistry) 11 (1969) 317) was modified to describe the effects of bottom sediment bioturbation, surface runoff from the catchment and suspended solids formation and sedimentation. The model input parameters are the effective diffusion coefficient in bottom sediments, depth of the completely mixed layer, the distribution coefficient in the sediment-water system, the runoff coefficient, sedimentation rate, and deposition density. Values of all these parameters can be independently estimated or measured in a short-term experiment. Given negligible runoff and sedimentation, the dynamics of radiocaesium in lake water is described by a simple equation with only one unknown parameter. This allows us to make long-term predictions on the basis of a series of measurements carried out during the relatively short period. The model was tested against 137Cs activity concentrations measured between 1993 and 1999 in Svyatoe lake in the Bryansk region of Russia. Calculated and measured activity concentrations are in good agreement.     

Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO2 pressure

Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO₂ pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 °C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO₂ and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH ± 12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.     

Characterisation of major component leaching and buffering capacity of RDF incineration and gasification bottom ash in relation to reuse or disposal scenarios

Thermal treatment of refuse derived fuel (RDF) in waste-to-energy (WtE) plants is considered a promising solution to reduce waste volumes for disposal, while improving material and energy recovery from waste. Incineration is commonly applied for the energetic valorisation of RDF, although RDF gasification has also gained acceptance in recent years. In this study we focused on the environmental properties of bottom ash (BA) from an RDF incineration (RDF-I, operating temperature 850-1000 °C) and a RDF gasification plant (RDF-G, operating temperature 1200-1400 °C), by evaluating the total composition, mineralogy, buffering capacity, leaching behaviour (both at the material’s own pH and as a function of pH) of both types of slag. In addition, buffering capacity results and pH-dependence leaching concentrations of major components obtained for both types of BA were analysed by geochemical modelling. Experimental results showed that the total content of major components for the two types of BA was fairly similar and possibly related to the characteristics of the RDF feedstock. However, significant differences in the contents of trace metals and salts were observed for the two BA samples as a result of the different operating conditions (i.e. temperature) adopted by the two RDF thermal treatment plants. Mineralogy analysis showed in fact that the RDF-I slag consisted of an assemblage of several crystalline phases while the RDF-G slag was mainly made up by amorphous glassy phases. The leached concentrations of major components (e.g. Ca, Si) at the natural pH of each type of slag did not reflect their total contents as a result of the partial solubility of the minerals in which these components were chemically bound. In addition, comparison of total contents with leached concentrations of minor elements (e.g. Pb, Cu) showed no obvious relationship for the two types of BA. According to the compliance leaching test results, the RDF-G BA would meet the limits of the Italian legislation for reuse and the European acceptance criteria for inert waste landfilling. RDF-I BA instead would meet the European acceptance criteria for non hazardous waste landfilling. A new geochemical modelling approach was followed in order to predict the leaching behaviour of major components and the pH buffering capacity of the two types of slags on the basis of independent mineralogical information obtained by XRD analysis and the bulk composition of the slag. It was found that the combined use of data regarding the mineralogical characterization and the buffering capacity of the slag material can provide an independent estimate of both the identity and the amount of minerals that contribute to the leaching process. This new modelling approach suggests that only a limited amount of the mineral phases that control the pH, buffering capacity and major component leaching from the solid samples is available for leaching, at least on the time scale of the applied standard leaching tests. As such, the presented approach can contribute to gain insights for the identification of the types and amounts of minerals that control the leaching properties and pH buffering capacity of solid residues such as RDF incineration and gasification bottom ash.     

Temporal variability in trace metal solubility in a paddy soil not reflected in uptake by rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.)

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.     

Multispecies and Multiscale Conservation Planning: Setting Quantitative Targets for Red‐Listed Lichens on Ancient Oaks

Abstract: Species occurrence in a habitat patch depends on local habitat and the amount of that habitat in the wider landscape. We used predictions from empirical landscape studies to set quantitative conservation criteria and targets in a multispecies and multiscale conservation planning effort. We used regression analyses to compare species richness and occurrence of five red‐listed lichens on 50 ancient oaks (Quercus robur; 120–140 cm in diameter) with the density of ancient oaks in circles of varying radius from each individual oak. Species richness and the occurrence of three of the five species were best explained by increasing density of oaks within 0.5 km; one species was best explained by the density of oaks within 2 km, and another was best predicted by the density of oaks within 5 km. The minimum numbers of ancient oaks required for “successful conservation” was defined as the number of oaks required to obtain a predicted local occurrence of 50% for all species included or a predicted local occurrence of 80% for all species included. These numbers of oaks were calculated for two relevant landscape scales (1 km² and 13 km²) that corresponded to various species responses, in such a way that calculations also accounted for local number of oaks. Ten and seven of the 50 ancient oaks surveyed were situated in landscapes that already fulfilled criteria for successful conservation when the 50% and 80% criteria, respectively, were used to define the level of successful conservation. For cost‐efficient conservation, oak stands in the landscapes most suitable for successful conservation should be prioritized for conservation and management (e.g., grazing and planting of new oaks) at the expense of oak stands situated elsewhere.     

Carbon speciation in municipal solid waste incinerator (MSWI) bottom ash in relation to facilitated metal leaching

The release of inorganic and organic contaminants from municipal solid waste incinerator (MSWI) bottom ash is controlled to a large extent by the release of dissolved organic carbon (DOC), and in particular by the reactive humic (HA) and fulvic acids (FA) subfractions of DOC. The properties of organic matter contributing to the release of DOC, HA and FA are, therefore, important for environmental risk assessment. In this study we have quantitatively measured the carbon speciation, and its relation with the leaching of Cu, in three fresh and carbonated MSWI bottom ash samples. Results show that up to only 25% of loss on ignition (LOI) consists of organic carbon (OC), while about 17% of OC in the three samples consists of HA and FA. Up to 50% of DOC in MSWI bottom ash leachates was identified as fulvic acid (FA). This value is substantially higher than previously estimated for these MSWI bottom ash samples and is consistent with the higher recovery of the new method that was applied. The results of this study imply that methods focusing on specific carbon fractions are more appropriate for assessment of environmentally relevant organic carbon species than the measurement of LOI.     

Availability and leaching of polycyclic aromatic hydrocarbons: Controlling processes and comparison of testing methods

We have studied the availability and leaching of polycyclic aromatic hydrocarbons (PAHs) from two contaminated materials, a tar-containing asphalt granulate (Sigma16 US-EPA PAHs 3412mg/kg) and gasworks soil (SigmaPAHs 900mg/kg), by comparing results from three typical types of leaching tests: a column, sequential batch, and two different availability tests. The sequential batch test was found to largely resemble the column test. However, the leaching of particularly the larger PAHs (>5 aromatic rings) was found to be enhanced in the batch test by up to an order of magnitude, probably due to their association with large DOC (dissolved organic carbon) molecules generated by the vigorous mixing. The release of PAHs in the two availability tests, in which the leaching is facilitated by either a high concentration of DOC or Tenax resin, was similar, although the latter test was easier to perform and yielded more repeatable results. The availability was much higher than the amount leached in the column and sequential batch tests. However, biodegradation had apparently occurred in the column test and the total amount of PAHs released by either leaching or biodegradation, 9% and 26% for asphalt granulate and gasworks soil, respectively, did equal the amount leached in the availability tests. Therefore, the availability was found to provide a relevant measure of the PAH fraction that can be released from the solid phase. These results stress the importance of using the available instead of the total amount of contaminant in the risk analysis of solid materials in utilization or disposal.     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.