Adsorption dynamique en phase liquide sur charbon actif : comparaison et simplification de différents modèles

L'adsorption en phase liquide sur charbon actif est un sujet très travaillé sur le plan expérimental et de plus en plus dans le domaine de la modélisation. Les tentatives de description des courbes de percée ou de fuite des filtres montrant la saturation du matériau adsorbant remontent aux travaux de BOHART et ADAMS en 1920. D'autres équations avec d'autres approximations ont été proposées par la suite (THOMAS 1944 ; DOLE et KLOLZ 1946), HUTCHINS (1973) ; plus récemment, WOLBORSKA (1989) ou CLARK (1987) ont proposé d'autres modèles. Nous avons essayé de faire le point sur ces différents modèles, de montrer leurs origines communes, souvent à partir des équations de BOHART et ADAMS, les approximations apportées limitant leur domaine d'application, les grandeurs qu'ils permettent de déterminer : capacité maximum d'adsorption, constante cinétique d'adsorption, vitesse de déplacement du front d'adsorption. De tous ces modèles, un seul (CLARK 1987) permet une bonne représentation des courbes de percée. Nous en avons proposé une linéarisaüon qui facilite la détermination des paramètres nécessaires au calcul des courbes de fuite. Tous ces modèles ont été testés sur les résultats expérimentaux obtenus pour l'adsorption d'un tensioactif anionique : le décylsulfonate de sodium et ceci sur cinq petites colonnes de hauteurs différentes de charbon actif. Le modèle de CLARK a également été appliqué à des résultats obtenus au laboratoire (El HANI, 1987) sur l'adsorption et la dégradation biologique des acides humiques sur un filtre de charbon de 1m de haut, sur une période beaucoup plus longue (1 mois) et avec des lavages du filtre. Ce modèle permet de calculer la part qui n'est pas simplement de l'adsorption rapide (dégradation biologique et adsorption lente).Low concentrations of organic contaminants are not easily removed by conventional treatment methods, but activated carbon bas a good affinity for various organics and is used in batch or column reactors.Much has been written concerning the prediction of the performance of powdered activated carbon (PAC) ; adsorptive capacity and equilibrium isotherms determined in « batch » reactor are proposed to simulate the performance of PAC for single or bisolute systems (DUSART et al. 1990, SMITH 1991). Some investigators have attempted to simulate column performance with mathematical models and the aim of this work is to present the principal models and verify how the different models are applied to break-through curves ; parameters which can be evaluated by the different equations will also be compared.As early as 1920 BOHART and ADAMS presented differential equations which govern the dynamics of the adsorption of vapours and gases on fixed beds and the final result, applied to the liquid-solid phase, yields the kinetic adsorption rate (k) and the maximum adsorption capacity (No) (eq. 3). By transposition to the liquid phase, we have calculated the concentration distribution in the bed (eq. 5) by using the kinetic constant k and the maximum adsorption capacity No obtained by equation 4; it was noted that only the low concentration range of the break-through curve can be used. Some approximations from DOLE and KLOTZ (1946) lead to the « Bed Depth/Service-Time (BDST) equation 7 proposed by HUTCHINS (1973) ; the service time of a column tb has a linear relationship with the bed depth Z (fig.3). The activated carbon efficiency No can be estimated and the adsorption rate constant calculated from the slope and the y-intercept.Recently, WOLBORSKA (1989) proposed a rectilinear equation InC/Co = At + B (eq. 10) for the initial segment of the break-through curve. The form of this equation is similar to equation (4) obtained tram the BOHART-ADAMS hypothesis. The mass transfer coefficient, ßa, the maximum adsorption capacity and the migration velocity v (eq.9) of the concentration fronts can be calculated from the constants A and B.The model developed by CLARK (1987) is based on the use of e mass-transfer concept in combination with the Freundlich isotherm (fig.4). The originality of this modal, in comparison to the others, consists in the existence of the equilibrium concentration Ce and the driving force equilibrium « C-Ce ». The general equation is equation (14). Two parameters A and r are determined by regression equations ; we proposed a simple method to calculate A and r by a linearization of the preceding equation (eq. 14). This is equation (16) In [(Co/C)n-1 -1] = In A -rt.Sodium decanesulfonate at a concentration of 20 mg ·l-1 was used as influent and activated powdered carton (200 ≤ ø ≤ 315 µm) as the fixed bed adsorbent layer to illustrate the comparison between the different models. The linear flow rates were 3.0 m . h-1 and the five columns tested were 3.1 ; 4.0 ; 7.5 ; 10.2 ; 12.5 cm high with a 1.45 cm2 cross section. The Freundlich isotherm equation (fig. 4) obtained in a batch system for an equilibrium time (t = 24 h for this activated carbon) gives a « n value » equal to 2.38.Figure 2 presents the experimental break-through curves obtained for the different bed heights ; by using equations (4 or 10) in the system (In C/Co, t) they are represented on the same figure by the dotted line. The agreement is only for the low values of C in the break-through curves.The coefficients A and B (table 1) are determined from the straight lines obtained with the low break-curve concentrations (fig. 1). The kinetic coefficient Sa, and the maximum capacity adsorption No are shown in table 1. The No value is similar to those obtained from the other equations. The migration velocity of the concentration fronts (r = 0,133 cm · h-1) is in good agreement with the experimental value (0,128 cm · h-1).The linearized Clark equation (16) gives a good representation of experimental results (fig. 6) alter the determination of A and r parameters (fig. 5 and table 2). With the use of the two parameters, the break-through curves have been recalculated (fig.6) and compared to experimental results. Their is good agreement. The A parameter is related to the depth Z of the adsorbant : A = Bez ·. B value can be determined with the different columns (fig.7).The Clark model can be applied to filers which have a biological activity ; the results obtained in the laboratory by EL HANI (1987) for the adsorption of humic acids (10 mg · l-1) on a 1m granular activated carton bed were analyzed by the Clark equation (fig. 8). The initial concentrations of humic acids are never obtained in the effluent because of biological degradation and/or slow adsorption in mesopores. From the difference in the area of the two curves, it is possible to calculate the supplementary biological degradation. For 95 cm of activated carbon in the column and after 800 h, the biological degradation represents 55 % of the total elimination. The percentage is constant alter 35 cm depth of the activated carton in agreement with the electon microscopy study that showed that the flora was only present in the 10 first centimeters.The use of this model is facilitated by our linearization and the case of particular phenomena : biological degradation or desorption. in the case of successive muld adsorbates fixation (REYDEMANEUF et al. to be published) can be studied and compared to the only adsorption phenomena.In conclusion, nome of the tested models lead to different parameters by using low break-through curve concentrations or others with the whole range of experimental points, but only one (CLARK) gives a good description of the break-through curves in our actual knowledge

Contribution à l'étude de la validité de différents modèles, utilisés lors de l'adsorption de solutés sur charbon actif

Les résultats de l'adsorption sur charbon actif en poudre de solutions aqueuses de différents composés organiques: phénol, aniline, nitrobenzène, acide salicylique, nitro-4 phénol, méthyl-2 dinitro-4,6 phénol, phénylalanine et tyrosine ont été traités à l'aide des équations de Langmuir, Elovich, Freundlich, Temkin, Fowler-Guggenheim, Hill et De Boer, Kiselev afin de déterminer divers paramètres d'équilibre: la capacité maximum d'adsorption, l'énergie d'adsorption, l'énergie d'interaction, les constantes d'équilibre adsorbat-adsorbant et les interactions (éventuelles) entre les molécules adsorbées.La relation de Temkin (3=RTt~Q In KoC permet de déterminer la variation de l'énergie d'adsorption ~Q et la constante Ko de l'équilibre (~3 est le degré de re- couvrement du charbon par le soluté, et C la concentration à l'équilibre). L'équa- tion de Fowler-Guggenheim KC=~3/(1~3) Exp (2 ~ W/RT) conduit à la déter- mination de l'énergie d'interaction W entre molécules adsorbées et à une constante d'équilibre K. Par contre, dans l'équation de Hill et de De Boer KlC=~/(1~)) Exp [~/(1~) - K2~/RTI, K2 représente une constante d'énergie d'interaction entre molécules adsorbées et, dans celle de Kiselev KIC=~3/[(1+ ~) (1 + Kn~3)]~ Kn est une constante de formation de complexe éventuel entre molécules adsorbées. On vérifie que l'application de la relation de Temkin est satisfaisante pour tous les composés étudiés et permet de les classer selon leur affinité sur le charbon mais les résultats obtenus en utilisant les équations suivantes (Fowler ...) montrent qu'il n'y aurait pas de formation de complexe ou d'interaction entre molécules adsorbées.Analysis of the results of adsorption from aqueous liquid media onto activated carbon can be carried out by different models based on thermodynamic principles. Classically the Langmuir (eq. 1), Freundlich or Elovich (eq. 4) isotherms are used, which lead to the determination of an experimental maximum capacity, qm, and a constant K, characteristic of the adsorbate-adsorbent interactions. The following equations (Table I) have been transposed from the vapour phase to the liquid phase. With the Temkin relation: [Theta]=RT/[Delta]QlnK[inf]0C (eq. 6), it is possible to determine the variation of adsorption energy, [Delta]Q, between the adsorbed molecules and the solid phase, and the equilibrium constant K[inf]0 ([Theta] is the degree of surface covering of the solid phase [Theta]=q/qm, q is the adsorption capacity). The Fowler-Guggenheim equation: KC=[[Theta]/(1-[Theta])] Exp (2[Theta]W/RT) (eq. 7) gives the interaction energy, W, between the adsorbed molecules and an equilibrium constant, K. The Hill and De Boer relation: K[inf]1C=[Theta]/(1-[Theta])] Exp [[Theta]/(1-[Theta]) -K[inf]2[Theta]/RT] (eq. 8) yields an energetic interaction constant K[inf]2 (J.mol-¹) characteristic of the interactions between the adsorbate molecules and an equilibrium constant, K[inf]1. In the Kiselev relation: K[inf]1C=([Theta]/[(1-[Theta]) (1 + K[inf]n[Theta]] (eq. 9), K[inf]n is a complex formation constant between adsorbed molecules and K[inf]1 is a constant relative to the adsorbate-adsorbent interaction. Linearization of the equations of Langmuir, and Elovich leads to qm and K values. For the Freundlich relation, if the experiments are made at constant Co and variable concentrations of adsorbent, the Freundlich relation can be transformed as relation (5): q=qm (C/Co)[sup]1/n). The value of qm and K are reported in the Table II. When the values obtained by the Elovich equation are very different from the Langmuir relation, they are not in concordance with the experimental adsorption isotherm as shown on the Figures 4, 5 and 6.A value of qm is necessary to calculate the ([Theta](=q/qm) of the Temkin, Hill-De Boer, Fowler- Guggenheim and Kiselev equations; [Theta] is calculated with the Langmuir value of qm: the linearized relations were tested for the following compounds: phenol, aniline, nitrobenzene, salicylic acid, 4-nitro phenol, 2-methyl-4,6 dinitro phenol, phenylalanine and tyrosine, studied at micromolar concentration. The results are shown in Table II. The Temkin linearization is of good quality for all the compounds; an example is given on the Figure 1. For the others (Figs. 2, 3), the linearization is not always verified (Hill-De Boer for phenylalanine: Fig. 3a) and the results are framed two times in the Table II.With the obtention of the two parameters [Delta][Theta], K K, W; K[inf]1, K[inf]2 and K[inf]1, K[inf]n, the isotherm can be recalculated. The results for some solutes are on Figures 4, 5, 6, 7, 8. Relatively poor results are obtained for Fowler-Guggenheim, Kiselev or Hill-De Boer models, where no association is present between the adsorbed molecules.The evolution of the variation of the adsorption energy ([Delta][Theta]) is reported on the Figure 9 for the different compounds. The greatest values are obtained for nitrobenzene and 4-nitro-phenol (+ 80, + 40 kJ.mol-¹ probably due to the presence of the nitro group). All the values are positive (exothermic reaction ( [Delta][Theta]=-[Delta]H)) showing the affinity of molecules for the activated carbon

Étude de la formation et de la stabilité des mousses chimiques de surface de la Vienne

Le recensement de la charge polluante rejetée dans la rivière Vienne (France) par les usines et les stations d'épuration de Limoges à Confolens a été effectué. Des campagnes de prélèvement et d'observations visuelles ont permis de localiser les lieux d'apparition de mousses en aval d'usines de fabrication de pâte à papier et de cartons. L'étude du pouvoir moussant des mélanges des deux principaux rejets polluants (papeterie et cartonnerie) a permis de mettre en évidence des phénomènes de synergie entre certains mélanges se traduisant à la fois par une augmentation du pouvoir moussant et de la stabilité de la mousse dans le temps. L'étude par « HPLC » montre l'apparition de pics supplémentaires confirmant l'interaction entre les constituants des rejets; le principal effluent a pu être suivi à l'aide de ses caractéristiques chimiques dans la rivière et dans les mousses jusqu'à Confolens.The study reported here considers of the formation and stability of foam on the Vienne river. Foaming is frequently encountered in relation to the discharge of industrial effluents, especially from the paper industry (CRAIG and al., 1990). Earlier papers have investigated the consequences of such discharges (NEILSON and al., 1990; KALLQVIST and al., 1989; SRIVASTAVA and al. 1988).The extent of foam formation is determined by a number of factors, including effluent composition, turbulence of the stream, etc. Foams stability requires the presence of long chain fatty acids, amine acids, tannins etc. Many industries discharge their effluents into the Vienne river (paper and cardboard industries, leather dressing plants and tanneries).An inventory of the main urban and industrial discharges has been established (Map 1). The effluents from the pulp, paper and cardboard industries provide the main pollution foad in terms of volume, COD, suspended solids (SS) and anionic surfactants.A visual survey allowed us to locus our investigations on the places where persistant foams appear, especially downstream of Saillat below the discharges from Aussedat Rey and SGPL (Picture 1), and below small waterfalls (Pont de Pilas, Chabanais, Ansac...). At Confolens, the foams are most stable and form stable drifting foam residues.Synergistic foaming effects have been reported due to the combination of polyamides and tannins (BIKERMAN, 1953). We have chosen to analyze the main effluents (Table 1) and their mixtures in relation to foaming (foaming capacity, foaming stability and surfactant analysis). The method used for foaming capacity determination was based on the hand shaking of 250 ml bottles. The stability of the foam was defined as the time for which the height of foam persists. Anionic surfactants were present at significant concentrations, varying from 1 mg/l (as sodium dodecyl sulphate) in the Aussedat Rey effluent to 4 mg/l in the SGPL effluent and 7 mg/l in the St Junien wastewater treatment plant effluent. The maximum foaming capacity was obtained for a 70/30 Aussedat Rey/SGPL effluent mixture (Fig. 1). The foaming capacity persists river time, remaining practically unchanged for three days. After 6 days, the maximum foaming capacity appears to be reduced. Foam stability is also maximum for the same 70/30 mixture (Fig. 2). After 6 days, the 50/50 and 70/30 mixtures can still produce 3 cm of foam that persist for 2 hours (Fig. 3).For HPLC analysis (20 µl samples), the effluents from AR and the effluents from SGPL (or the mixture of the two) were diluted in 10 times their volume of distilled water prior to analysis. Concerning the mixture 95 % AR - 5 % SGPL (95/5) the peak that characterizes the SGPL effluent starts appearing and growing at 6.76 min. With the proportions : 90/10 and 70/30, its retention time respectively diminishes from 6.34 min. to 5.58 min. Moreover an extra peak appears with the 70/30 mixture at 5.02 min. This extra peak is at its highest at 4.96 min. for a 50/50 mixture. At the same time the initial AR peak is decreasing. It is thus confirmed that one or more constituent: are formed on mixing the two effluents, as indicated by the synergistic effect described earlier for the foam capacity and stability analysis.Anionic surfactants were analyzed in the Vienne river (Fig. 5). Their concentration dramatically increase at point (4) (Pont de Pilas), just below the discharges from AR and SGPL. When the river flow increases, dilution masks the phenomenon. A drastic decrease in pollution appears in August when the industrial activity is reduced because of holidays (Fig. 7).The HPLC Vienne river analysis (Fig. 5) shows an important peak of pollution at point (4) (Pont de Pilas) characteristic of the AR effluent. At Chabanais point (5), the ARISGPL ratio is 95/5 and the peak of SGPL appears, perhaps, et 6.12 min (in the diluted effluents in the same ratio 95/5, it appears at 6.34 min). At Confolens (10), the intensity has diminished (after two days) and the Confolens foams are the same as those produced by a river sample without concentrated effect. No appreciable degradation has occurred, since the height of the peaks point 10 is similar as those of the chromatogram of point (5) in accord with the literature (LESZKIEWICZ and KINNER, 1988 ; COTE and OTIS, 1989)

Neuroprotective Properties of Topiramate in the Lithium- Pilocarpine Model of Epilepsy

ABSTRACT The lithium-pilocarpine model reproduces the main characteristics of human temporal lobe epilepsy. After status epilepticus (SE), rats exhibit a latent seizure-free phase characterized by development of extensive damage in limbic areas and occurrence of spontaneous recurrent seizures. Neuroprotective and antiepileptogenic effects of topiramate were investigated in this model. SE was induced in adult male rats by LiCl (3 mEq/kg) followed 20 h later by pilocarpine (25 mg/kg). Topiramate (10, 30, or 60 mg/kg) was injected at 1 and 10 h of SE. Injections were repeated twice a day for six additional days. Another group received two injections of diazepam on the day of SE and of vehicle for 6 days. Neuronal damage was assessed at 14 days after SE by cell counting on thionin-stained sections. Occurrence of spontaneous recurrent seizures (SRS) was videorecorded for 10 h per day in other groups of rats. In diazepam-treated rats, the number of neurons was dramatically reduced after SE in all subregions of hippocampus and layers II-IV of ventral cortices. At all doses, topiramate induced a 24 to 30% neuroprotection in layer CA1 of hippocampus (p Ͻ 0.05). In CA3b, the 30-mg/kg dose prevented neuronal death. All rats subjected to SE became epileptic. The latency (14 -17 days) to and frequency of SRS were similar in topiramate-and diazepam-treated rats. The high mortality in the 30 mg/kg topiramate group (84%) was possibly the result of interaction between lithium and topiramate. In conclusion, topiramate displayed neuroprotective properties only in CA1 and CA3 that were not sufficient to prevent epileptogenesis

Promoting bioengineered tooth innervation using nanostructured and hybrid scaffolds

The innervation of teeth mediated by axons originating from the trigeminal ganglia is essential for their function and protection. Immunosuppressive therapy using Cyclosporine A (CsA) was found to accelerate the innervation of transplanted tissues and particularly that of bioengineered teeth. To avoid the CsA side effects, we report in this study the preparation of CsA loaded poly(lactic-co-glycolic acid) (PLGA) nanoparticles, their embedding on polycaprolactone (PCL)-based scaffolds and their possible use as templates for the innervation of bioengineered teeth. This PCL scaffold, approved by the FDA and capable of mimicking the extracellular matrix, was obtained by electrospinning and decorated with CsA-loaded PLGA nanoparticles to allow a local sustained action of this immunosuppressive drug. Dental re-associations were co-implanted with a trigeminal ganglion on functionalized scaffolds containing PLGA and PLGA/cyclosporine in adult ICR mice during 2 weeks. Histological analyses showed that the designed scaffolds did not alter the teeth development after in vivo implantation. The study of the innervation of the dental re-associations by indirect immunofluorescence and transmission electron microscopy (TEM), showed that 88.4% of the regenerated teeth were innervated when using the CsA-loaded PLGA scaffold. The development of active implants thus allows their potential use in the context of dental engineering. Statement of Significance Tooth innervation is essential for their function and protection and this can be promoted in vivo using polymeric scaffolds functionalized with immunosuppressive drug-loaded nanoparticles. Immunosuppressive therapy using biodegradable nanoparticles loaded with Cyclosporine A was found to accelerate the innervation of bioengineered teeth after two weeks of implantation

Foliar lead uptake by lettuce exposed to atmospheric fallouts

Metal uptake by plants occurs by soil−root transfer but also by direct transfer of contaminants from the atmosphere to the shoots. This second pathway may be particularly important in kitchen gardens near industrial plants. The mechanisms of foliar uptake of lead by lettuce (Lactuca sativa) exposed to the atmospheric fallouts of a lead-recycling plant were studied. After 43 days of exposure, the thoroughly washed leaves contained 335 ± 50 mg Pb kg−1 (dry weight). Micro-X-ray fluorescence mappings evidenced Pb-rich spots of a few hundreds of micrometers in diameter located in necrotic zones. These spots were more abundant at the base of the central nervure. Environmental scanning electron microscopy coupled with energy dispersive X-ray microanalysis showed that smaller particles (a few micrometers in diameter) were also present in other regions of the leaves, often located beneath the leaf surface. In addition, submicrometric particles were observed inside stomatal openings. Raman microspectrometry analyses of the leaves identified smelter-originated Pb minerals but also secondary phases likely resulting from the weathering of original particles. On the basis of these observations, several pathways for foliar lead uptake are discussed. A better understanding of these mechanisms may be of interest for risk assessment of population exposure to atmospheric metal contamination

Electrophilic Organoiridiunn(III) Pincer Complexes on Sulfated Zirconia for Hydrocarbon Activation and Functionalization

Single-site supported organometallic catalysts bring together the favorable aspects of homogeneous and heterogeneous catalysis while offering opportunities to investigate the impact of metal–support interactions on reactivity. We report a (dmPhebox)Ir(III) (dmPhebox = 2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl) complex chemisorbed on sulfated zirconia, the molecular precursor for which was previously applied to hydrocarbon functionalization. Spectroscopic methods such as diffuse reflectance infrared Fourier transformation spectroscopy (DRIFTS), dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR) spectroscopy, and X-ray absorption spectroscopy (XAS) were used to characterize the supported species. Tetrabutylammonium acetate was found to remove the organometallic species from the surface, enabling solution-phase analytical techniques in conjunction with traditional surface methods. Cationic character was imparted to the iridium center by its grafting onto sulfated zirconia, imbuing high levels of activity in electrophilic C–H bond functionalization reactions such as the stoichiometric dehydrogenation of alkanes, with density functional theory (DFT) calculations showing a lower barrier for β-H elimination. Catalytic hydrogenation of olefins was also facilitated by the sulfated zirconia-supported (dmPhebox)Ir(III) complex, while the homologous complex on silica was inactive under comparable conditions

High-Throughput Experimentation, Theoretical Modeling, and Human Intuition: Lessons Learned in Metal–Organic-Framework-Supported Catalyst Design

We have screened an array of 23 metals deposited onto the metal-organic framework (MOF) NU-1000 for propyne dimerization to hexadienes. By a first-of-its-kind study utilizing data-driven algorithms and high-throughput experimentation (HTE) in MOF catalysis, yields on Cu-deposited NU-1000 were improved from 0.4 to 24.4%. Characterization of the best-performing catalysts reveal conversion to hexadiene to be due to the formation of large Cu nanoparticles, which is further supported by reaction mechanisms calculated with density functional theory (DFT). Our results demonstrate both the strengths and weaknesses of the HTE approach. As a strength, HTE excels at being able to find interesting and novel catalytic activity; any a priori theoretical approach would be hard-pressed to find success, as high-performing catalysts required highly specific operating conditions difficult to model theoretically, and initial simple single-atom models of the active site did not prove representative of the nanoparticle catalysts responsible for conversion to hexadiene. As a weakness, our results show how the HTE approach must be designed and monitored carefully to find success; in our initial campaign, only minor catalytic performances (up to 4.2% yield) were achieved, which were only improved following a complete overhaul of our HTE approach and questioning our initial assumptions

Tissue-specific inducible expression of antimicrobial peptide genes in Drosophila surface epithelia

The production of antimicrobial peptides is an important aspect of host defense in multicellular organisms. In Drosophila, seven antimicrobial peptides with different spectra of activities are synthesized by the fat body during the immune response and secreted into the hemolymph. Using GFP reporter transgenes, we show here that all seven Drosophila antimicrobial peptides can be induced in surface epithelia in a tissue-specific manner. The imd gene plays a critical role in the activation of this local response to infection. In particular, drosomycin expression, which is regulated by the Toll pathway during the systemic response, is regulated by imd in the respiratory tract, thus demonstrating the existence of distinct regulatory mechanisms for local and systemic induction of antimicrobial peptide genes in Drosophila