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Oil leaks (or spills) into the aquatic environment are considered a natural disaster and a severe environmental problem for the entire planet. Samples of polyurethane (PU) composites were prepared with high specific surface area carbon nanotubes (CNT) to investigate crude oil sorption. Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), density measurements, and mechanical compression tests were used to characterize the polyurethane-carbon PU-CNT prepared samples. The spongy composites exhibited good mechanical behavior and a contact angle of up to 119°. The oleophilic character resulted in increased hydrophobicity, a homogeneous oil distribution inside the sponge, and a sorption capacity in a water/oil mixture of 41.82 g/g. Stress-strain curves of the prepared samples showed the good mechanical properties of the sponge, which maintained its stability after more than six sorption desorption cycles. The CNT-PU composites may prove very effective in solving oil pollution problems.
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Enteric viruses are widely spread in water environments, some being harmful for human communities. Regular epidemics highlight the usefulness of analysing such viruses in wastewaters as a tool for epidemiologists to monitor the extent of their dissemination among populations. In this context, CNovel™ Powdered Activated Carbon (PAC) was chosen for its high porosity and high adsorption capacity to investigate sorbent ability to be used as part of of virus detection probes. Self-supported PAC Foils (PAC-F), PAC coated Brushes (PAC-B) and PAC Sampler (PAC-S) were used to prospect PAC efficacy in virus adsorption and above all, the feasibility of virus retrieval from them, allowing to further analysis such as molecular analysis quantification. Aiming at the development of a field-operational tool, PAC saturation and reusability were also investigated, as well as PAC-polarisation effect on its adsorption capacity. Our results pointed out that sorbent-based probes exhibited a high adsorption efficacy of spiked Murine Norovirus (MNV-1) in bare 0.1 M NaCl solution (>90 % for PAC-B and >86 % for PAC-F at ≈107 genome unit virus concentration), with no saturation within our experimental framework. On the other hand, polarisation assays using PAC-F as electrode, did not demonstrate any adsorption improvement. Experiments on PAC probes reusability suggested that they should be used three times at the most for a maximum efficiency. Values of virus retrieval were low (up to 11 % with PAC-B and up to 14 % with PAC-F in 0.1 M NaCl virus suspensions), illustrating the need for the techniques to be improved. A preliminary field assay using PAC-S, demonstrated that our catch-and-retrieve protocol yielded to the detection of autochthonous human Norovirus Genogroup I (NoV GI) and Adenovirus (AdV), in wastewaters suggesting its promising application as virus detection tool in such high loaded and complex waters.
Asunto(s)
Contaminantes Químicos del Agua , Purificación del Agua , Adsorción , Animales , Carbón Orgánico , Humanos , Ratones , Aguas Residuales , Purificación del Agua/métodosRESUMEN
Persulfate activation by heterogeneous catalysts based on transition metals is of interest in textile effluent treatment processes. Thus, iron-rich electrocoagulation sludge has been thermally treated to obtain new catalysts. The characterization of this catalyst by X-ray diffraction revealed the presence of FeAl2O4 nanoparticles active in the decomposition of persulfate into sulfate radicals (SO4â¢-). The efficiency of catalyst/persulfate was monitored during the methylene blue (MB) solution discoloration. The effects of temperature, pH, initial MB concentration, catalyst dose and persulfate dose were also studied. MB removal catalytic activity showed around 94% discoloration and 45.7% TOC reduction after 180 minutes batch reaction at pH = 4.0 (catalyst dose: 0.5 g/L, persulfate dose: 1 g/L; initial MB concentration: 20 mg/L). This catalyst reuse further confirmed its catalytic potential as a discoloration rate of about 82.45% was obtained after five cycles. The biodegradability monitoring measured by the carbon oxidation state (COS) has revealed a remarkable and continuous degradation of organic compounds. The EPR tests revealed that this catalytic reaction generates the radical species responsible for the degradation of MB. Finally, these results show that this catalyst from the thermal activation of electrocoagulation sludge is capable of decomposing persulfate to degrade bioresistant compounds such as textile dyes.
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Azul de Metileno , Contaminantes Químicos del Agua , Catálisis , Electrocoagulación , Hierro/química , Azul de Metileno/química , Oxidación-Reducción , Aguas del Alcantarillado , Contaminantes Químicos del Agua/químicaRESUMEN
This study aims at determining the optimal conditions for pollutants removal in wastewater using Eichhornia crassipes (E. crassipes) and Pistia stratiotes (P. stratiotes) as appropriate aquatic plants for a post-treatment by phytoremediation. From factors such as residence time, plant density and initial PO43- concentration, four responses, i.e. the removal efficiency of PO43-, NO3-, NH4+ and the chemical oxygen demand (COD) were followed, using complete factorial design. After validation of the regression models by the statistical analyses, optimal conditions were obtained by using the global desirability function. Global desirabilities of 0.96 and 0.97 were respectively obtained for E. crassipes and P. stratiotes, for a residence time of 30 days, a plant density of 60 feet/m2 and an initial PO43- concentration of 10 mg/L. Using E. crassipes, this corresponds to the elimination of 94.2% of PO43-; 93.3% of NO3-; 95.0% of NH4+ and 63.6% of COD. In the case of P. stratiotes, 93.9% of PO43-; 83.4% of NO3-, 99.5% of NH4+ and 84.4% of COD were removed. Finally, under the used conditions, E. crassipes are able to better eliminate phosphorus and nitrates, while P. stratiotes are very effective in removing NH4+ and COD.
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Araceae , Eichhornia , Contaminantes Ambientales , Contaminantes Químicos del Agua , Biodegradación Ambiental , Contaminantes Ambientales/análisis , Aguas Residuales/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
Defluoridation of groundwater was performed in a batch reactor using bivalve shell powder (BSP) as adsorbent. The physicochemical characteristics of BSP, studied by Fourier Transform Infrared, X-ray Diffraction and Inductively Coupled Plasma-Optical Emission Spectrometry after dissolution, have shown that BSP was mainly composed of crystalline CaCO3 (â¼97.8%). The effects of pH, initial fluoride concentration, adsorbent dose and contact time on the adsorption capacity of BSP were investigated. For an initial fluoride concentration of 2.2 mg/L and with 16 g/L of BSP, after 8 hours of treatment, 27.3% were eliminated at pH 7.5 versus 68% at pH 3, highlighting the efficiency of the adsorption process. The difference in adsorption capacity as a function of pH was correlated to the pHpzc of the BSP, which was equal to 8.2. Thus, at pH below pHpzc, electrostatic attraction between the fluoride anions and the positively charged adsorbent could justify the adsorption mechanism. Fittings of experimental data have evidenced that the adsorption kinetics were of pseudo-second order whereas the adsorption isotherms were of Langmuir type. The chemical precipitation of calcium fluoride was also revealed to occur upon release of Ca2+ from partial dissolution of CaCO3 in acidic conditions.
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Exoesqueleto/química , Bivalvos , Fluoruros/química , Agua Subterránea/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Adsorción , Animales , Aniones/análisis , Concentración de Iones de Hidrógeno , Cinética , Difracción de Rayos XRESUMEN
This work emphazises the importance of the solubilizing conditions for the elaboration of chitosan hydrogel beads, which were produced using electromagnetic laminar jet breakup technology, resulting in dried porous beads by further freeze-drying. Paramaters such as the acid nature and concentration (acetic, formic, citric, lactic, maleic and malic, 0.1 to 0.5â¯mol·L-1), the chitosan concentration (2 to 5â¯wt%) and composition of the gelation bath (NaOH, with or without EtOH) were studied. Viscosity versus strain rate measurements were carried out on chitosan acidic solutions and the viscoelastic behaviour was studied on hydrogels. The solutions exhibiting the highest viscosities led to the stiffest macrohydrogels, as a result of chitosan carboxylate interactions. Specific surface areas of the freeze-dried beads were determined in the range from 12 to 107â¯m2·g-1. Their internal texture was observed by Scanning Electron Microscopy. Water uptake was also measured for further use in the field of water purification.
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Ácidos/química , Materiales Biocompatibles/química , Quitosano/química , Hidrogeles/química , Compuestos Orgánicos/química , Algoritmos , Modelos Teóricos , Porosidad , Reología , Soluciones , ViscosidadRESUMEN
The thermodynamic of the adsorption of seven organic pollutants, namely benzotriazol, bisphenol A, caffeine, carbamazepine, diclofenac, ofloxacin, and pentachlorophenol, was studied on a microporous-activated carbon fabric. The isosteric adsorption quantities (Gibbs energy, enthalpy, and entropy variations) at high coverage ratio (around 1 mmol/g) have been determined from the adsorption isotherms at three temperatures (13, 25, and 40 °C). The adsorption heats at very low coverage (about 10-5 mmol/g) have been measured by flow micro calorimetry. The experimental adsorption energies were correlated to the adsorbate-adsorbent and the adsorbate-solvent interaction energies calculated by simulations using the COSMO-RS model. The main role of the van der Waals forces in the adsorption of the studied molecules was established. The bulkier the adsorbate is, the lower the adsorption Gibbs energy variation at high coverage deduced from the isotherms. The heterogeneity of the adsorption sites was brought out by calorimetric measurements. At high coverage, a physisorption phenomenon was observed. At very low coverage, high values of the adsorption heats were found (ranging from -58 to -110 kJ/mol), except for pentachlorophenol characterized by an athermal adsorption controlled by Pi-anions interactions.
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Carbón Orgánico/química , Termodinámica , Adsorción , Calorimetría , TextilesRESUMEN
Glassy carbon particles (millimetric or micrometric sizes) dispersions in water were treated by ultrasound at 20kHz, either in a cylindrical reactor, or in a "Rosette" type reactor, for various time lengths ranging from 3h to 10h. Further separations sedimentation allowed obtaining few nanoparticles of glassy carbon in the supernatant (diameter <200nm). Thought the yield of nanoparticle increased together with the sonication time at high power, it tended to be nil after sonication in the cylindrical reactor. The sonication of glassy carbon micrometric particles in water using "Rosette" instead of cylindrical reactor, allowed preparing at highest yield (1-2wt%), stable suspensions of carbon nanoparticles, easily separated from the sedimented particles. Both sediment and supernatant separated by decantation of the sonicated dispersions were characterized by laser granulometry, scanning electron microscopy, X-ray microanalysis, and Raman and infrared spectroscopies. Their multiscale organization was investigated by transmission electron microscopy as a function of the sonication time. For sonication longer than 10h, these nanoparticles from supernatant (diameter <50nm) are aggregated. Their structures are more disordered than the sediment particles showing typical nanometer-sized aromatic layer arrangement of glassy carbon, with closed mesopores (diameter â¼3nm). Sonication time longer than 5h has induced not only a strong amorphization (subnanometric and disoriented aromatic layer) but also a loss of the mesoporous network nanostructure. These multi-scale organizational changes took place because of both cavitation and shocks between particles, mainly at the particle surface. The sonication in water has induced also chemical effects, leading to an increase in the oxygen content of the irradiated material together with the sonication time.
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BACKGROUND: Sulfonated polyimides (SPIs) are considered as the promising alternatives to Nafion as membrane materials for the polymer electrolyte membrane (PEM). They generally exhibit high ionic conductivity, good mechanical properties, excellent thermal and chemical stabilities. The six-membered ring, naphthalenic anhydride-based SPIs, not only exhibit superior chemical and thermo-oxidative stabilities but are also more resistant to hydrolysis than their five-membered phthalic anhydride-based SPIs. The composites based on napthalenic polyimides are also significantly stable in high temperature environment and show better stability to hydrolysis. Incorporation of inorganic fillers into organic polymers has gained tremendous attention and these new materials are called organic-inorganic hybrids. Few patents related to the synthesis and performance PEM materials have been reviewed and cited. Keeping in view the importance of sulfonated polyimide based nanocomposites as potential membrane materials for PEM in fuel cell, we have synthesized SPIs clay based nanocomposite as potential membrane material. The objective of this work was to synthesize clay based SPIs thin films which could be used as membrane materials in PEM fuel cell for energy applications. Methods/Experimental: At the first step the nanometric sheets of vermiculite clay prepared via sonication was surface modified by grafting 3-APTES. Then the SPI was synthesized via one-step high temperature direct imidization method, which serve as a matrix material. The organo modified VMT was dispersed via sonication in the SPI matrix. Four different sets of organic-inorganic nanocomposite membranes thin films, having VMT contents in the range of 1 to 7 wt.% were prepared by casting, curing and acidification route. RESULTS: The synthesis of SPIs clay based thin films were carried out at three different steps and fully characterized. The synthesis of SPIs and SPIs clay based thin films were analyzed via different analytical techniques. The XRD analysis tells the successful dispersion of clay in SPI matrix. Different physiochemical tests were conducted for the analysis of these membranes such as water uptake, hydrolytic stability, ion exchange capacity (IEC), dimensional changes and oxidative stability, to check their suitability as membrane materials for PEM. The proton conductivity of these membranes were measured via impedance spectroscopy which discloses three different active regions responsible for proton conduction. The activation energies of the membranes were higher at lower temperature and reaches to 8.2 kJ/mol at higher temperature (90oC). CONCLUSION: The synthesis of sulfonated polyimide/clay (SPI/clay) based organic-inorganic nanocomposite membranes were achieved successfully. The membrane display good hydrolytic, thermal and oxidative stability at elevated temperature. The proton conductivity of the membrane display an increase together with the frequency but decreases with temperature. Therefore some more efforts are required to achieve high degree of functionalization of both organic and inorganic components, for the "future" PEMs to avoid deterioration and to get improved performance.
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The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures.
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Bromuros/química , Líquidos Iónicos/química , Solventes/química , Contaminantes Químicos del Agua/química , Adsorción , Cationes/química , Carbón Orgánico/química , Compuestos Heterocíclicos/química , Cinética , Temperatura , TermodinámicaRESUMEN
The effects of temperature, time, solvent and sonication conditions under air and Argon are described for the preparation of micron and sub-micron sized vermiculite particles in a double-jacketed Rosett-type or cylindrical reactor. The resulting materials were characterized via X-ray powder diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared (FTIR) Spectroscopy, BET surface area analysis, chemical analysis (elemental analysis), Thermogravimetry analysis (TGA) and Laser Granulometry. The sonicated vermiculites displayed modified particle morphologies and reduced sizes (observed by scanning electron microscopy and laser granulometry). Under the conditions used in this work, sub-micron sized particles were obtained after 5h of sonication, whereas longer times promoted aggregation again. Laser granulometry data revealed also that the smallest particles were obtained at high temperature while it is generally accepted that the mechanical effects of ultrasound are optimum at low temperatures according to physical/chemical properties of the used solvent. X-ray diffraction results indicated a reduction of the crystallite size along the basal direction [001]; but structural changes were not observed. Sonication at different conditions also led to surface modifications of the vermiculite particles brought out by BET surface measurements and Infrared Spectroscopy. The results indicated clearly that the efficiency of ultrasound irradiation was significantly affected by different parameters such as temperature, solvent, type of gas and reactor type.
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The effect of ultrasounds on the surface of metallic plates with cubic faced centered (Al, Ag, Cu) or hexagonal (Zn) structure was studied. Treated surfaces were strongly attacked: a micrometric roughness and a superficial oxidation (characterized by roughness measurements and scanning electron microscopy) were induced. X-ray diffraction analyses showed a preferential reorientation of the maximum density planes for both crystallographic structures.