Physical and chemical characterisation of crude meat and bone meal combustion residue: “waste or raw material?”

As a result of the recent bovine spongiform encephalopathy (BSE) crisis in the European beef industry, the use of animal by-product is now severely controlled. Meat and bone meal (MBM) production can no longer be used to feed cattle and must be safely disposed of or transformed. Main disposal option is incineration, producing huge amounts of ashes the valorisation of which becomes a major concern. The aim of this work is to characterise MBM combustion residue in order to evaluate their physical and chemical properties to propose new valorisation avenues. The thermal behaviour of crude meat and bone meal was followed by thermogravimetric analysis (TGA) and (24 wt.%) inorganic residue was collected. The resulting ashes were characterised by powder X-ray diffraction (XRD), particle size distribution, specific surface area (BET), scanning electron microscopy (SEM) couple with energy disperse X-ray analysis (EDX). Elemental analysis revealed the presence of chloride, sodium, potassium, magnesium with high level of phosphate (56 wt.%) and calcium (31 wt.%), two major constituents of bone, mainly as a mixture of Ca10(PO4)6(OH)2 and Ca3(PO4)2 phases. The impact of combustion temperature (from 550 to 1000 °C) on the constitution of ashes was followed by TGA, XRD and specific surface measurements. We observed a strong decrease of surface area for the ashes with crystallisation of calcium phosphates phases without major changes of chemical compositio

Perspectives on blended learning through the on-line platform, LabLessons, for Chemistry

The effectiveness of blended learning was evaluated through the integration of an online chemistry platform, LabLessons. Two modules, Formation of Hydrogen and Titration, were designed by college mentors alongside classroom chemistry teachers to engage and allow high school students to better comprehend these scientific topics. The pre-lab modules introduced the students to experiments they were expected to perform in class the following day. The modules consisted of an introduction as well as either a visualization and/or simulation specific to each topic. Students and teachers who utilized LabLessons were surveyed to establish a preliminary research on the use of technology in classrooms. Student and teacher surveys demonstrated LabLessons to be an interactive and helpful tool to improve students' understanding of conceptual ideasPeer Reviewe

Stabilisation of heavy metal containing dusts by reaction with phosphoric acid: study of the reactivity of fly ash

International audienceWater-washed fly ash was reacted with phosphoric acid in order to transform available heavy metals into insoluble metal phosphate compounds. The temperature, pH and concentration of free phosphate were monitored during the first 80 min of reaction. Phosphoric acid reacted rapidly with second order kinetics and an apparent rate constant of 0.015 l/(mol s m(2)). Analysis of the evolution of the concentrations of other major elements of fly ash shows that the reaction follows a dissolution-precipitation type mechanism. The solubility of trace heavy metals tends to increase at low pH values. Various heat and mass transfer coefficients are derived and help understand the phosphate stabilisation procedure and design industrial reactors for this purpose. Calcium phosphates are formed which can trap heavy metals in a stable apatite mineral structure

Laboratory scale study of an industrial phosphate and thermal treatment for polluted dredged sediments

International audienceDredged sediments are being chemically treated with phosphoric acid on an industrial scale. The effectiveness of the treatment was evaluated by performing the chemical reaction in a tubular reactor, followed by convective drying and maturation of the treated sediment at ambient temperature and finally thermal destruction of the organic matter by calcinations (500 degrees C-900 degrees C). The influence of acid concentration and calcination temperature on the specific surface area of the sediment was investigated. The stabilization of the heavy metals was evaluated by leaching tests and sequential extraction procedures. The phosphoric acid treatment is effective in reducing heavy metal mobility, a prerequisite for recycling the sediments in various construction materials

Characterization of LiFePO4/C Cathode for Lithium Ion Batteries

International audienceLiFePO4/C was synthesized from a mixture of different precursors of Li, Fe, and C by solid-state reaction. The initial mixture obtained was heated in different calcination conditions under inert atmosphere. The precursor of LiFePO4 doped with carbon was studied using different techniques such as thermal analysis, chemical and physical characterizations, and Mosbauer spectroscopy. A calculation of the crystallinity of the final product with two different methods is also presented. The chemical analysis techniques used were IRTF, XRD, and SEM. This characterization confirmed that we obtained a well-crystallized LiFePO4/C in all the operating conditions tested. The SEM showed aggregation and sintering during the calcination process, which were confirmed by the particle-size distribution measurements and by the physical characterizations. Mosbauer spectroscopy was used to determine the quantity of Fe(II) and Fe(III) contained in the final product. Our calcination conditions did not significantly modify the quantity of the two oxidation states

Removal of aqueous lead ions by hydroxyapatites: Equilibria and kinetic processes

Issu de : WasteEng05 Conference 1st international conference on engineering for waste treatment, Albi, FRANCE, 17-19 May 2005International audienceThe capacity of hydroxyapatite (HAp) to remove lead from aqueous solution was investigated under different conditions, namely initial metal ion concentration and reaction time. The sorption of lead from solutions containing initial concentrations from 0 to 8000 mg/L was studied for three different HAp powders. Soluble Pb and Ca monitoring during the experiment allows characterizing the mechanism of lead uptake. Dissolution of calcium is followed by the formation of a solid solution, PbxCa10−x(PO4)6(OH)2, with a Ca/P ratio decreasing continuously. Langmuir–Freundlich classical adsorption isotherms modeled adsorption data. The adsorption capacities calculated from this equation vary from 330 to 450 mg Pb/g HAp for the different solids. Modeling of the sorption process allows to determine theoretical saturation times and residual lead concentrations at equilibrium

Using E. coli NfsA as a model to improve our understanding of enzyme engineering

There is a substantial gap between the levels of enzyme activity that nature can achieve and those that scientists can evolve in the lab. This suggests that conventional directed evolution techniques involving incremental improvements in enzyme activity may frequently fail to ascend even local fitness maxima. This is most likely due to the difficulty for step-wise evolutionary approaches in effectively retaining mutations that are beneficial in combination with one another, but on an individual basis are neutral or deleterious (i.e., exhibit positive epistasis). We sought to determine whether a superior enzyme identified using a simultaneous mass site directed mutagenesis approach could have been identified using a step-wise approach. We conducted simultaneous mass randomisation of eight key active site residues in Escherichia coli NfsA, a nitroreductase enzyme that has diverse applications in biotechnology. Using degenerate codons, we generated a diverse library containing 394 million unique variants. We then applied a powerful positive selection using chloramphenicol which is toxic to E. coli but can be detoxified via nitro-reduction. This has enabled us to recover a diverse range of highly active nitroreductase variants. For two of the most active variants, we have created all possible combinations of single mutations. This allowed us to examine whether a step-wise mutagenesis pathway could have also yielded these enzymes. As anticipated, we identified complex epistatic interactions between residues in these enzyme variants. We have also investigated the “black-box” effect of enzyme engineering, examining the consequences that evolving NfsA towards one specialist activity had on the other promiscuous activities of NfsA. Variants generated in this study have also had practical applications, in particular for targeted cell ablation in zebrafish. We have identified NfsA variants that are highly active with nil-bystander prodrugs that can selectively ablate nitroreductase expressing cells without harm to adjacent cells. In ongoing work, our lead variants are being evaluated for their utility in transgenic zebrafish models of degenerative disease

Phosphatation de résidus minéraux

International audienceThe incineration of municipal solid waste generates mineral residues which contain soluble chlorides and heavy metal pollutants. The mineral residue is currently landfilled after a cement solidification. An alternative treatment, the new patented by Solvay process uses phosphoric acid to stabilise mineral residue by the formation of stable minerals such as calcium phosphates which are insoluble in natural environments and can incorporate heavy metals inside their crystalline structure. Two different water-washed municipal solid waste incinerator mineral residues are investigated during the phosphate treatment. Phosphoric acid reacts exothermically with mineral residues with rapid kinetics of the dissolution-precipitation type. Second order rate is observed with respect to the phosphate concentration and activation energies for the phosphate reaction are found to be small (near 20 kJ/mol). Mineral residues react with phosphoric acid mainly as calcium carbonate does. Precipitated amorphous calcium phosphates coat the more inert particles (silicoaluminates, silicates, and calcium sulphates…). The two mineral residues with different compositions show similar behaviour. This indicates the phosphate stabilisation procedure can be widely applied. This chemical treatment can be considered as a first essential step in the effective insolubilisation of extractable trace heavy metals in a mineral material that could find in the future an beneficial reuse after further processing as secondary raw materialSolvay a breveté un nouveau procédé de stabilisation de résidus minéraux contaminés par des métaux lourds et des composés organiques dont l’une des étapes fondamentales est le traitement chimique à l’acide phosphorique. Son objectif est de former des phosphates de calcium de grande stabilité chimique et thermique, capables d’incorporer dans leur structure cristalline les métaux lourds. L’étude de la cinétique de phosphatation montre que la réaction est exothermique. Les phosphates calciques formés enrobent les particules les plus inertes. L’énergie d’activation faible (20 kJ/mol), caractéristique d’une réaction acide-base, est proche de celle de la réaction avec le carbonate de calcium. Les expérimentations menées et les paramètres observés indiquent que la phosphatation peut être généralisée pour tous les résidus minéraux et constituer une première étape dans l’insolubilisation effective des métaux lourds. Ceci permet d’envisager pour le futur une possible revalorisation des résidus minéraux phosphatés et calcinés comme matière première secondaire

Simultaneous randomisation of eight key active site residues in E. coli NfsA to generate superior nitroreductases for prodrug activation

There is a substantial gap between the levels of enzyme activity Nature can evolve and those that scientists can engineer in the lab. This suggests that conventional directed evolution techniques involving incremental improvements in enzyme activity may frequently fail to ascend even local fitness maxima. This is most likely due to an inability of step-wise evolutionary approaches to effectively retain mutations that are beneficial in combination with one another, but on an individual basis are neutral or even slightly deleterious (i.e., exhibit positive epistasis). To overcome this limitation, we are seeking to “jump” straight to an enzyme with peak activity by conducting simultaneous mass randomisation of eight key active site residues in Escherichia coli NfsA, a nitroreductase enzyme that has several diverse applications in biotechnology. Using degenerate codons, we generated a diverse library containing 425 million unique variants. We then applied a powerful selection system using either or both of two recently identified positive selection compounds, which has enabled us to recover a diverse range of highly active nitroreductase variants. These have been screened against a panel of prodrug substrates to identify variants that are improved with specific prodrug substrates of interest. A primary focus has been developing nitroreductases as tools for targeted cell ablation in zebrafish. The basic system involves co-expression of a nitroreductase and fluorescent reporter under the control of a cell type specific promoter in a transgenic fish. Expression of the nitroreductase selectively sensitises target cells to a prodrug which, following nitroreduction, yields a cytotoxic compound that causes precise targeted cell ablation. We have identified several nil-bystander prodrugs that are able to selectively ablate nitroreductase expressing cells with no harm to nearby cells, and have paired these with highly specialised NfsA variants to improve the efficacy and accuracy of cell ablation. We have also screened our mass-randomisation libraries to recover nitroreductases that have non-overlapping prodrug specificities, to be used in a multiplex cell ablation system. This expands upon the previous system, by using pairs of selective nitroreductases and two different prodrugs to facilitate independent ablation of multiple cell types. For example, we have identified a specialist NfsA variant that has activity for tinidazole and not for metronidazole, achieved by including metronidazole as a simultaneous counter-selection during the initial positive selection process. This elegant positive/negative selection eliminated activity with metronidazole, while still ensuring that some level of nitroreductase activity was retained overall

Vaporisation et/ou stabilisation de métaux lourds au cours du traitement thermique de déchet : cas des déchets ménagers solides et des boues de dragage

International audienceThe fate of heavy metals is one of the main problems that operators of solid waste incineration plants have to deal with to reduce the overall environmental impact of the plant and of the ultimate residue. The question is : should the process conditions avoid toxic metal vaporisation, thus increasing their concentration in bottom ash ? Or, on the contrary, should they favour metal release in combustion gases, thus requiring the highest performance air pollution control (APC) systems and stabilising materials? In order to examine the industrial impact of these two possibilities, we are currently developing two complementary approaches.The first one is concerned with the fate of heavy metals in incineration of municipal wastes and sludge, and coal combustion. We characterised physico-chemically the ultimate residues, and we developed a complete thermodynamic and experimental study of the behaviour of heavy metals in waste incinerators and coal combustors. We developed a general method (inverse method) to identify the kinetics of vaporisation of heavy metals from the on-line analysis of the exhaust gas of solid waste incineration. The second approach deals with the transformation of heavy metals contained in fly ash and dredged materials into phosphate components, using orthophosphate as stabilising agent.The technique involves a chemical treatment followed by a thermal treatment (sintering), that reduce the leachability of heavy metals. Better knowledge of thermal treatment of polluted wastes should lead to safer processes and residue reuse opportunities.La maîtrise des émissions de métaux lourds (ML) est un des problèmes majeurs qui se posent aux opérateurs des UIOM pour réduire l'impact environnemental des incinérateurs puis des déchets ultimes. Nos équipes développent deux approches complémentaires autour de la vaporisation des métaux et de leur stabilisation. Dans la première approche, après avoir caractérisé les résidus ultimes, nous avons développé une étude thermodynamique et expérimentale du comportement des ML dans les procédés de combustion et incinération. Nous avons développé une méthode générale (méthode inverse) permettant d'identifier la cinétique de vaporisation des métaux à partir de l'analyse en ligne des fumées d'incinérateur. La deuxième approche s'intéresse à la stabilisation par les orthophosphates des ML contenus dans les cendres volantes et dans les matériaux de dragage. La technique consiste en un traitement chimique suivi d'un frittage, qui limitent la vaporisation et réduisent la lixiviabilité des ML. Ces connaissances scientifiques doivent aider à une meilleure maîtrise des traitements thermiques de déchets pollués et une meilleure valorisation matière des résidus