État du développement technologique en matière d'enlèvement des métaux des effluents industriels

Cette étude trace un profil des diverses technologies utilisées et en développement pour la séparation et/ou la récupération des métaux dans les effluents industriels. Les principes de fonctionnement de ces technologies sont abordés, ainsi que leurs avantages et limites d'utilisation. Les procédés d'enlèvement et de récupération des métaux comprennent les techniques de précipitation (formation d'hydroxydes, de carbonates, de sulfures, etc.) et coprécipitation (sels de fer et d'aluminium, etc.), d'adsorption (sable, cellulose, charbon activé, pyrite, ciment, lignite, mousse de tourbe, sciure de bois, etc.) et de biosorption (bactéries, levures, moisissures, algues marines et d'eaux douces), d'électrodéposition et d'électrocoagulation, de cémentation, de séparation par membranes (osmose inverse et électrodialyse), d'extraction par solvant (acides carboxyliques, amines aliphatiques ou aromatiques, acides aminés, composés phénoliques, phosphates alkyl, etc.), et d'échange d'ions (résines naturelles et synthétiques). La précipitation ou la coprécipitation représentent les procédés les plus largement utilisés et étudiés pour l'enlèvement des métaux des effluents industriels, suivis des techniques d'adsorption. Les procédés plus sophistiqués tels que l'électrodéposition, l'extraction par solvant, la séparation par membranes et l'échange d'ions, bien que largement utilisés dans les procédés métallurgiques, sont relativement peu employés et examinés pour le traitement des effluents industriels. La biosorption a fait l'objet de plusieurs travaux de recherche au cours des dernières années et représente une option intéressante pour le traitement de divers types d'effluents contenant de faibles concentrations en métaux. Finalement, le recyclage et la gestion optimale des effluents constitue une avenue de plus en plus suivie par les industries soucieuses de satisfaire aux nouvelles réglementations et législations.This study is dedicated to the review of the different technologies used and evaluated for the removal and/or recovery of metals from industrial effluents. The principles involved in these technologies are discussed, as well as the advantages and limits associated with these processes. The metal removal and recovery processes include the following techniques: precipitation, adsorption and biosorption, electrowinning and electrocoagulation, cementation, membrane separations, solvent extraction and ion exchange.Precipitation and coprecipitation are the most used and studied methods for metal removal from industrial waste waters. The method of precipitation used most often to remove metals from waste water consists of precipitating them in the form of hydroxides. The usual procedure involves the addition of chemicals such as lime (CaO or Ca(OH)2), Mg(OH)2, NaHCO3, Na2 CO3, (NH4)2 CO3, NaOH or NH4 OH. The precipitation of metals by carbonates or sulphides is an effective alternative to hydroxide precipitation. The use of carbonates allows the precipitation of metals to occur at pH values lower than those necessary with the hydroxides. Moreover, the precipitates thus formed are denser and have better characteristics of solid-liquid separation. Precipitation by sulphides is normally carried out with reagents such as: Na2 S, NaHS, H2 S or FeS. In acidic media, the lower solubility of metal sulphides (Cd, Co, Cu, Cr, Ni, Mn, Zn, etc.), makes it possible to reach concentrations lower than those obtained by precipitation as hydroxides. Coprecipitation with aluminum and iron salts is also an effective means for the removal of metals from effluents.Adsorption methods are also widely applied and examined for this purpose. However, in most cases the use of adsorbents requires an effluent neutralization step. Indeed, the neutralization of acid effluents must take place to allow their disposal in sewerage systems. A wide variety of adsorbents can be employed, both organic and inorganic: aluminum or iron oxides, sand, activated carbon, mixtures of coal and pyrite, iron particles, gravel or crushed brick, cement, etc. Studies have demonstrated the possibility of eliminating metals by adsorption on vegetable matter: peat moss, sawdust and wood bark, etc. Chitin and chitosan, two natural polymers that are abundant in the cell walls of fungi and shellfish, also have excellent properties of metal fixation. The utilization of different agricultural by-products (peanut skins, coconuts, corn cobs, onions skins, tea leaves, coffee powder, canola meal, etc.) for metal adsorption has also been proposed.Biosorption has been intensively studied in recent years as an economical treatment for metal recovery from dilute industrial effluents. Biosorption implies the use of live or dead biomass and/or their derivatives, which adsorb the metal ions with the ligands or functional groups located on the external surface of the microbial cells. Capacities for metal adsorption on various types of biomass (bacteria, yeasts, fungi, marine and freshwater algae) have been evaluated. The microorganisms used for the metal adsorption step must usually be immobilized in a matrix or in an easily recoverable support. The immobilizing agents or matrices most usually employed are alginate, polyacrylamine, polysulphone, silica gel, cellulose and glutaraldehyde.Electrowinning is a well-established technology that is widely employed in the mining and metallurgical industries (heap leaching, acid mine drainage, etc.), in metal transformation industries (wastes from plating and metal finishing), and in the electronics and electrical industries for the removal and/or the recovery of metals in solution. Many metals (Ag, Au, Cd, Co, Cr, Cu, Ni, Pb, Sn and Zn) present in the effluents can be recovered by electrodeposition using insoluble anodes.Electrocoagulation is another electrochemical approach, which uses an electrical current to remove several metals in solution. In fact, the electrocoagulation systems can be effective in removing suspended solids, dissolved metals, tannins and dyes. The contaminants present in waste water are maintained in solution by electrical charges. When these ions and the other charged particles are neutralized with ions of opposite electric charge, provided by a electrocoagulation system, they become destabilized and precipitate in a form that is usually very stable.Cementation is a type of precipitation method implying an electrochemical mechanism. In this process, a metal having a higher oxidation potential passes into solution (e.g., oxidation of metallic iron, Fe(0), to ferrous iron, Fe(II)) to replace a metal having a lower oxidation potential. Copper is the metal most frequently separated by cementation. However, the noble metals (Ag, Au and Pd), as well as As, Cd, Ga, Pb, Sb and Sn, can also be recovered in this manner.Reverse osmosis and electrodialysis are two processes using semipermeable membranes applicable to the recovery of metal ions. In electrodialysis, selective membranes (alternation of cation and anion membranes) fit between the electrodes in electrolytic cells. A continuous electrical current and the associated ion migrations, allow the recovery of metals. The techniques of membrane separation are very efficient for the treatment of dilute waste waters.The metallurgical industry has used solvent extraction for many years for a broad range of separations. This technique is employed today for the removal of soluble metals (Cd, Cr, Co, Cu, Ni, Mo, U, V, Zn, etc.) from waste water. Separation is carried out in contact with an immiscible organic phase to form salts or complex compounds, which give a favorable solubility distribution between the aqueous and organic phases. Various types of reagents can be used for the extraction: carboxylic acids, aliphatic or aromatic amines, amino acids, alkyl phosphates, phenolic compounds. The non-selective removal of metal contaminants in aqueous solutions can be obtained with a whole range of organic reagents. Promising new reagents have been proposed recently for the selective extraction of metals, such as Cd, Co, Cr and Zn.Ion exchangers are insoluble substances having in their molecular structure acidic or basic groups able to exchange, without modification of their physical structure, the positive or negative ions fixed at these groups. The first ion exchangers used were natural substances containing aluminosilicates (zeolites, clays, etc). Nowadays, the most-used ion exchangers are mainly organic in nature (resins). For the extraction of metals, the removal of cations in solution is usually done with the sulphonic acid group (-SO3- H+) of a polystyrene resin, or, with a chelating resin containing iminodiacetate functional groups. Ion exchange has recently received considerable attention for the separation and concentration of metals from waste water. These developments are especially applicable to the plating and metal transformation industries, for the removal of Cr, Co, Cu, Cd, Ni, Fe and Zn.The more sophisticated processes, such as electrowinning, solvent extraction, membrane separations and ion exchange, although frequently used in metallurgical processes, are less popular for wastewater treatment than are precipitation methods. Finally, recycling and optimal management of effluents constitutes an approach more and more widely applied by industries to satisfy new environmental regulations and laws

Covariant energy density functionals with and without tensor couplings at the Hartree-Bogoliubov level

Background: The study of additional terms in functionals is relevant to better describe nuclear structure phenomenology. Among these terms, the tensor one is known to impact nuclear structure properties, especially in neutron-rich nuclei. However, its effect has not been studied on the whole nuclear chart yet. Purpose: The impact of terms corresponding to the tensor at the Hartree level, is studied for infinite nuclear matter as well as deformed nuclei, by developing new density-dependent functionals including these terms. In particular, we study in details the improvement such a term can bring to the description of specific nuclear observables. Methods: The framework of covariant energy density functional is used at the Hartree-Bogoliubov level. The free parameters of covariant functionals are optimized by combining Markov-Chain-Monte-Carlo and simplex algorithms. Results: An improvement of the RMS binding energies, spin-orbit splittings and gaps is obtained over the nuclear chart, including axially deformed ones, when including tensors terms. Small modifications of the potential energy surface and densities are also found. In infinite matter, the Dirac mass is shifted to a larger value, in better agreement with experiments. Conclusions: Taking into account additional terms corresponding to the tensor terms in the vector-isoscalar channel at the Hartree level, improves the description of nuclear properties, both in nuclei and in nuclear matter

Commensurate-Incommensurate Magnetic Phase Transition in Magnetoelectric Single Crystal LiNiPO4_4

Neutron scattering studies of single-crystal LiNiPO$_4$ reveal a spontaneous first-order commensurate-incommensurate magnetic phase transition. Short- and long-range incommensurate phases are intermediate between the high temperature paramagnetic and the low temperature antiferromagnetic phases. The modulated structure has a predominant antiferromagnetic component, giving rise to satellite peaks in the vicinity of the fundamental antiferromagnetic Bragg reflection, and a ferromagnetic component giving rise to peaks at small momentum-transfers around the origin at $(0,\pm Q,0)$. The wavelength of the modulated magnetic structure varies continuously with temperature. It is argued that the incommensurate short- and long-range phases are due to spin-dimensionality crossover from a continuous to the discrete Ising state. These observations explain the anomalous first-order transition seen in the magnetoelectric effect of this system

Alpha-particle formation and clustering in nuclei

The nucleonic localization function has been used for a decade to study the formation of alpha-particles in nuclei, by providing a measure of having nucleons of a given spin in a single place. However, differences in interpretation remain, compared to the nucleonic density of the nucleus. In order to better understand the respective role of the nucleonic localization function and the densities in the alpha-particle formation in cluster states or in alpha-decay mechanism, both an analytic approximation and microscopic calculations, using energy density functionals, are undertaken. The nucleonic localization function is shown to measure the anti-centrifugal effect, and is not sensitive to the level of compactness of the alpha-particle itself. It probes the purity of the spatial overlap of four nucleons in the four possible (spin, isospin) states. The density provides, in addition, information on the compactness of an alpha-particle cluster.Comment: 8 pages, 5 figure

Multi-level Policy Coalitions An Interpretative Model Of Water Conflicts ιn The Americas

This article proposes an analytical approach to conflicts and policy-making related to urban water management based on multi-level policy coalitions. This is necessary to articulate four main issues. First, the repositioning of social and political struggles for access to water, along with policy variables. Second, the analysis of the effects of ecological transition, including climate change. Third, the reincorporation of these struggles and challenges in a multi-level approach. Finally, the enquiry into the apparent contradiction, in contemporary policymaking. The article proposes a definition of multi-level coalitions as collective preference systems that influence the content of policies (ideas/advocacy, decisions, policy tools) and their implementation, groups of actors that arise from engagement in policy issues. In the first section, the article presents the objectives of research on urban water management in the Americas, within the framework of which this analytical approach by multi-level coalitions is fashioned. In the second section, the article details four analytical issues. In the third section, it gives a definition of multi-level coalitions.19415317

Essential role of STAT5a in DCIS formation and invasion following estrogen treatment

Ductal carcinoma in situ (DCIS) is one of the earliest stages of breast cancer (BCa). The mechanisms by which DCIS lesions progress to an invasive state while others remain indolent are yet to be fully characterized and both diagnosis and treatment of this pre-invasive disease could benefit from better understanding the pathways involved. While a decreased expression of Caveolin-1 (Cav-1) in the tumor microenvironment of patients with DCIS breast cancer was linked to progression to invasive breast cancer (IBC), the downstream effector(s) contributing to this process remain elusive. The current report shows elevated expression of Signal Transducer and Activator of Transcription 5a (STAT5a) within the DCIS-like lesions in Cav-1 KO mice following estrogen treatment and inhibition of STAT5a expression prevented the formation of these mammary lesions. In addition, STAT5a overexpression in a human DCIS cell line (MCF10DCIS.com) promoted their invasion, a process accelerated by estrogen treatment and associated with increased levels of the matrix metalloproteinase-9 (MMP-9) precursor. In sum, our results demonstrate a novel regulatory axis (Cav-1♦STAT5a♦MMP-9) in DCIS that is fully activated by the presence of estrogen. Our studies suggest to further study phosphorylated STAT5a (Y694) as a potential biomarker to guide and predict outcome of DCIS patient population

Buoyant-thermocapillary instabilities of differentially heated liquid layers

URL: http://www-spht.cea.fr/articles/T95/103 Instabilités d'écoulements thermocapillaires en présence de gravitéInternational audienceThe stability of buoyant-thermocapillary-driven flows in a fluid layer subjected to a horizontal temperature gradient is analysed. Our purpose is the modelization of recent experimental results obtained for a fluid of Prandtl number Pr=7, by Daviaud and Vince [Phys. Rev. E, 4432 (1993)] who observed a transition between traveling waves and stationary rolls when the height of fluid is increased. Our model takes into account several effects which were examined separately in previous studies. The relative importance of buoyancy and thermocapillarity is controlled by the ratio W of Marangoni number to Rayleigh number. The fluid layer is bounded below by a rigid plane whose temperature varies linearly along the direction of the thermal gradient. A Biot number is introduced to describe heat transfer at the top free surface. Our stability analysis establishes the existence of a transition between stationary and oscillatory modes when W exceeds a value ${\rm W}_0$ which is function of the Biot number. Moreover, two types of oscillatory modes have been identified which differ by the range of variation of their critical parameters (wave number, frequency, angle of propagation) versus W

Microscopic description of α\alpha, 2α2\alpha, and cluster decays of 216,218^{216,218}Rn and 220−224^{220-224}Ra

Alpha and cluster decays are analyzed for heavy nuclei located above $^{208}$Pb on the chart of nuclides: $^{216,218}$Rn and $^{220-224}$Ra, that are also candidates for observing the $2 \alpha$ decay mode. A microscopic theoretical approach based on relativistic Energy Density Functionals (EDF), is used to compute axially-symmetric deformation energy surfaces as functions of quadrupole, octupole and hexadecupole collective coordinates. Dynamical least-action paths for specific decay modes are calculated on the corresponding potential energy surfaces. The effective collective inertia is determined using the perturbative cranking approximation, and zero-point and rotational energy corrections are included in the model. The predicted half-lives for $\alpha$-decay are within one order of magnitude of the experimental values. In the case of single $\alpha$ emission, the nuclei considered in the present study exhibit least-action paths that differ significantly up to the scission point. The differences in alpha-decay lifetimes are not only driven by Q values, but also by variances of the least-action paths prior to scission. In contrast, the $2 \alpha$ decay mode presents very similar paths from equilibrium to scission, and the differences in lifetimes are mainly driven by the corresponding Q values. The predicted $^{14}$C cluster decay half-lives are within three orders of magnitudes of the empirical values, and point to a much more complex pattern compared to the alpha-decay mode.Comment: 9 pages, 13 figure