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Mine wastes have been considered as a source of heavy metal (HM) contamination in the environment and negatively impact many important ecosystem services provided by soils. Plants like Miscanthus, which tolerate high HM concentrations in soil, are often used for phytoremediation and provide the possibility to use these soils at least for the production of energy crops. However, it is not clear if plant growth at these sites is limited by the availability of nutrients, mainly nitrogen, as microbes in soil might be affected by the contaminant. Therefore, in this study, we investigated in a greenhouse experiment the response of ammonia-oxidizing microbes in the root-rhizosphere complex of Miscanthus × giganteus grown in soils with different levels of long-term arsenic (As) and lead (Pb) contamination. Quantitative PCR of the ammonia monooxigenease gene (amoA) was performed to assess the abundance of ammonia-oxidizing bacteria (AOB) and archaea (AOA) at two different points of plant growth. Furthermore, bulk soil samples before planting were analyzed. In addition, terminal restriction fragment length polymorphism (T-RFLP) analysis was used to investigate the diversity of archaeal amoA amplicons. Whereas high concentrations of As and Pb in soil (83 and 15 g/kg, respectively) resulted independent from plant growth in a clear reduction of AOA and AOB compared to the control soils with lower HM contents, in soils with contamination levels of 10 g/kg As and 0.2 g/kg Pb, only AOB were negatively affected in bulk soil samples. Diversity analysis of archaeal amoA genes revealed clear differences in T-RFLP patterns in response to the degree of HM contamination. Therefore, our results could clearly prove the different response patterns of AOA and AOB in HM-contaminated soils and the development of archaeal amoA phylotypes which are more tolerant towards HMs in soil samples from the areas that were impacted the most by mining waste, which could contribute to functional redundancy of ammonia-oxidizing microbes in soils and stability of nitrification pattern.

This work characterises the mineral fraction of EPS extracts obtained using eight different methods from two activated sludges by total mineral content determination, Fourier Transformed Infrared spectrometry and with scanning electron microscopy coupled with an EDX probe. Despite EPS dialysis, the EPS extracts displayed a mineral fraction between 2% and 40% of the EPS dry weight depending on the extraction method used. The main mineral elements found in the EPS extract were Ca, Mg, Na, K, Al, Fe, Mn, P, Si and S, but their contents were strongly affected by the extraction method used. Some of the minerals are associated with the organic molecules within the EPS. The presence of mineral particles of various compositions and structures (clays, quartz or carbonate) in the EPS extract with a wide range in size was clearly demonstrated. Moreover, the association of metallic elements with the mineral particles in the EPS extract was highlighted., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The redox potential (Eh) is a key parameter for controlling the release of elements from solid materials. Nevertheless, this parameter is seldom taken into account during risk assessment studies within any regulatory framework. We studied the incidence of redox changes to the solid materials using two batch procedures: i) a gradient of redox conditions obtained using sodium ascorbate solutions at various concentrations; ii) N(2) bubbling in water. These experiments were performed on two Mn-rich slag samples coming from a pyrometallurgical plant that recycles alkaline batteries. Both samples differed slightly in their chemical composition and solid characterization (i.e. presence of Mn oxide) and presented different behaviours. The present study focused on the release of the main slag elements (i.e. Mn and Si) chosen as indicators of the dissolution of primary silicate phases. Solid phase analyses (SEM-EDS and XRD) were coupled with the monitoring of elements in leachates in order to understand their behaviour and the mechanisms involved. The results indicated that the solid composition plays an important role in the release mechanisms. The presence of Mn oxide enhanced the mobilization of Mn in the greatest reducing conditions (-320 ± 5 mV/SHE), to the extent that 42% of the total Mn was leached. This demonstrated the significance in studying the solid phases (using SEM-EDS and XRD) before and after any leaching experiment. From a laboratory practice point of view, it was easier to use sodium ascorbate and allowed, in our case, greater reducing conditions to be reached., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

In the present study, different complementary leaching tests were applied to a Mn-rich slag sample that was not thoroughly studied until now, in order to understand the potential mobility of the elements (Mn, Si, Fe, Ca, K, Mg, Al) within it. Several standard leaching tests (EN 12457-1 and -2, and TCLP) were carried out in order to compare results to regulatory values: the Mn-rich slag studied could be considered as 'inert' waste with respect to the release of the main trace metallic elements (Cu, Ni and Zn). In order to have a better understanding of the environmental behaviour of the Mn-rich slag constituents, other tests were performed. These experiments revealed that the dissolution of the Mn-rich slag was favoured for pH < or = 6. The mobility of the major elements was governed by the solubility of the primary solid phases and the precipitation of secondary minerals. The Visual MINTEQ modelling allowed the leaching results to be completed. From an environmental point of view, the reuse of this slag in acidic conditions has to be rejected due to the dissolution of the main solid phase.

A Mn-rich slag sample coming from a pyrometallurgical plant recycling alkaline batteries was submitted to environmental conditions during one year. After crushing, the slag was buried in topsoil and the leachate was periodically collected in order to monitor the leached amounts of metallic elements (ME). Results evidenced a low release of the slag constituents (Mn: < 0.01%). The SEM/EDS investigations did not show alteration features supposing a weak dissolution of the primary phases (tephroite, bustamite and leucite). The modification of the pH induced by the slag enhanced the mobility of soil components and of the organic matter, particularly in the vicinity of the soil/slag contact zone. This suggested that the slag indirectly influenced the ME mobility through the organic matter and colloidal transports. The comparison with a classical laboratory column test evidenced the underestimation of the leached amounts due to the differences of operational conditions., (Copyright 2010 Elsevier Ltd. All rights reserved.)

The extracellular polymeric substances (EPS) extracted from four anaerobic granular sludges contain an important mineral fraction (20-77% of the EPS dry weight). The composition of the mineral fraction of EPS depends strongly of the extraction method applied and to a lesser extend of the origin of the anaerobic sludge. Centrifugation, sonication, and heating extraction procedures yield a similar mineral composition. However, extraction using a cationic exchange resin (CER) leads to an increase of the Na(+) content in the EPS extract because the CER promotes an exchange of divalent and trivalent inorganic elements in the EPS extracts toward Na(+). Chemical extraction protocols were also shown to contaminate the EPS extracts by impurities or carry over of the extractant itself (e.g., ethanol). A part of the mineral fraction is bound to the EPS organic matter and structures the EPS matrix in the granules. Scanning electron microscopic analysis (SEM-EDX) showed that, in addition, solid particles such as CaCO(3) and Ca(5)OH(PO(4))(3) containing various metallic elements (i.e., Al, Fe, Cu, Mn...) are present in the EPS as well. This inorganic fraction, too often neglected in EPS studies, can influence the physicochemical properties of EPS.

The present study deals with the sorption of Cd(II) and Pb(II) by exopolymeric substances (EPS) extracted from activated sludges or pure bacterial strains. The percentage of sorbed metal increases with the concentration of the EPS-water solution. Pb(II) always presents a higher affinity than Cd(II) for EPS. For the EPS extracted from pure bacterial strains, only one global binding constant from a simple equilibrium sorption model, may be used to assess the effect of microbial products such as EPS on Cd(II) and Pb(II) speciation or mobility in the environment. However, for EPS extracted from activated sludges, the wide variation of the global binding constants determined for Cd(II) and Pb(II) do not permit such a simple approach. The differences in sorption to metals between the two types of EPS (bacterial, activated sludges) could be explained by the differences in EPS composition: organic macromolecules, as well as the nature of the mineral fraction.