Multicomponent Adsorption of Pesticides onto Activated Carbon Fibers

The adsorption equilibria of pesticides and metabolites (atrazine, deethylatrazine, deisopropylatrazine and simazine) are studied onto activated carbon fibers –ACF– with a broad pore size distribution (32% mesopore volume, 68% micropore volume). Mono-and multi-component isotherms have been determined for low concentrations, from 0.23×10⁻⁶ to 9.52×10⁻⁶ mol L⁻¹. Single solute isotherms, modeled by Freundlich and Langmuir models, tend to prove the influence of the adsorbate's solubility in the adsorption capacity of activated carbon fibers. Binary solute isotherms confirm the strong influence of pesticide solubility on the competitive adsorption mechanism: the competition is higher in the case of adsorbates of different solubilities (atrazine and DEA or DIA for example). Multicomponent experimental data were modeled by extended Langmuir-based equations and the Ideal Adsorbed Solution theory. Whereas the first ones failed to model accurately binary adsorption due to restrictive hypothesis, the IAS model showed a good agreement between experimental and predicted data. It emphasised also the difficulty in satisfying the hypothesis of the model in the case of highly adsorbed compounds. Finally, the simultaneous adsorption of atrazine and NOM (in a natural water, DOC = 18.2 mg L⁻¹) shows no adsorption competition effects between natural organic matter and atrazine. This is due to the presence of secondary micropores (0.8–2 nm) and mesopores in the ACF, which limit a pore blockage phenomenon by NOM.     

Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds: Kinetics,isotherms, mass transfer,thermodynamics and process design

The adsorption of Basic Magenta II onto H₂SO₄ activated immature Gossypium hirsutum seeds was analysed using Ho, modified Freundlich, Sobkowsk–Czerwi, Blanchard, Elovich, Avrami, and modified Ritchie kinetic models by nonlinear regression-sum of normalized errors analysis. The goodness of fit was evaluated with coefficient of determination and root mean square error. The good agreement of experimental data to Avrami second-order model indicated that the mechanism of adsorption followed multiple kinetic orders. The Avrami second-order mechanism was applied to predict the rate constant of sorption and the equilibrium capacity and subsequently the obtained equilibrium adsorption capacities were utilized to find the equilibrium concentrations. Langmuir, Freundlich, Temkin, Sips and Hill isotherms were investigated to understand the nature of adsorption with the help of nonlinear regression analysis. Both Sips and Hill isotherms were best fit to the adsorption equilibrium data showing the homogeneous adsorption on the heterogeneous surface of carbon and the positive co-operative manifestations of the Basic Magenta II molecules. The mass transfer study depicted the details such as mass transfer coefficient, intra-particle diffusion rate, pore diffusion coefficient, and film diffusion coefficient. The adsorption process was found to be controlled by film diffusion. The thermodynamic parameters like, Gibbs free energy change, enthalpy change, entropy change and isosteric heat of adsorption confirmed the endothermic, feasible and spontaneous nature of adsorption. A single stage batch adsorber was designed using Sips isotherm constants to estimate the amount of carbon required for desired purification.     

Separating surface and solvent effects and the notion of critical adsorption energy in the adsorption of phenolic compounds by activated carbons

A modified form of the Freundlich equation in which the solute equilibrium concentration is normalized with respect to the solute solubility is analyzed and applied to adsorption isotherms of phenol, 4-nitrophenol, 4-chlorophenol, and 2-chlorophenol at different values of pH on commercial activated carbon before and after oxidation. The analysis confirms the importance of normalizing the solute equilibrium concentration when analyzing the adsorption isotherms, and it is suggested that a parameter, K(F10), obtained by taking 10% solubility as the reference point when applying the Freundlich equation, is probably the best comparative estimate of the relative adsorption capacity of the carbon for different phenolic compounds. In combination with the Freundlich exponent, n(F), estimates of the adsorption capacity at any other reference point can then be obtained. Analysis of the experimental results also indicates a need to distinguish between two regimes of adsorption, characterized by an adsorption energy, E(ads), greater than or less than a critical value, E(ca). When E(ads) > E(ca), the shape of the adsorption isotherm is determined by solute-solid interactions. On the other hand, when E(ads) < E(ca), solute-solution interactions become more important.     

Human urine certified reference material CZ 6010: creatinine and toluene metabolites (hippuric acid and o-cresol) and a benzene metabolite (phenol)

A reference material for the biological monitoring of occupational exposure to toluene, benzene and phenol was prepared. O-cresol and hippuric acid (metabolites of toluene) are used for the biological monitoring of occupational exposure to toluene. Phenol, a metabolite of benzene, is used for the biological monitoring of exposure to benzene, but phenol can of course also be used as an indicator of exposure to phenol as well. The reference material (RM) used for the determination of these metabolites was prepared by freeze-drying pooled urine samples obtained from healthy persons occupationally exposed to toluene and those taking part in an inhalation experiment. Tests for homogeneity and stability were performed by determining urine concentrations of o-cresol, hippuric acid, creatinine and phenol. To investigate the stability of the RM, the urinary concentrations of o-cresol and phenol were monitored for eighteen months using GC and HPLC, while those of hippuric acid and creatinine were followed for five and six years, respectively, using HPLC. Analysis of variance showed that the concentrations did not change. The certified concentration values (and their uncertainties) of the substances in this reference material (phenol concentration c=6.46±0.58 mg l⁻¹; o-cresol concentration c=1.17±0.15 mg l⁻¹; hippuric acid concentration c=1328±30 mg l⁻¹; creatinine concentration c=0.82±0.10 g l⁻¹) were evaluated via the interactive statistical programme IPECA.     

Removal of Phenol by Using Montmorillonite,Clinoptilolite and Hydrotalcite

This work is to study the removal of phenol from aqueous solutions by adsorption using three different adsorbents, clinoptilolite, montmorillonite, and hydrotalcite (HT). Except for montmorillonite, the other adsorbents were treated. Clinoptilolite was modified using cetyltrimethylammonium bromide (CTAB) and hydrotalcite was calcined by heating to 550C. Adsorption isotherms of phenol on all of the mentioned adsorbents was determined by using the batch equilibration technique and indicated that, the adsorption behavior could be modelled by using the Modified Freundlich equation. The differences observed in the isotherms were explained by the variations in adsorbent-adsorbate interactions under the effects of the different surface structures of adsorbents and the pH dependent ionization behavior of phenol. Calcined hydrotalcite (HTC) was found to be the best among the studied adsorbents since it can adsorb 52% of phenol from a solution containing initially 1 g/L phenol for the 1/100 adsorbent solution ratio while the others can adsorb only 8% of phenol for the same concentration and adsorbent solution ratio.     

Rice husk ash as an adsorbent for methylene blue—effect of ashing temperature

Utilization of one waste material to control pollution caused by another is of high significance in the remediation of environmental problems. Rice husk, an abundantly available agricultural waste, can be used as a low cost adsorbent for dyes and heavy metals in effluent streams. The possible utilization of rice husk ash as an adsorbent for methylene blue dye from aqueous solutions has been investigated. Ash samples from husks of two origins were prepared at different temperatures and their physical, chemical spectroscopic and morphological properties were determined. XRD, FTIR and SEM were some of the techniques adopted for the characterization. The samples were also analyzed for bulk density, pH, nitrogen adsorption properties and lime reactivity. Experiments of methylene blue adsorption on the ash samples were conducted using batch technique and a comparative study was made. Results were analyzed using linear, Langmuir and Freundlich isotherms. The values of separation factor indicate that most of the ash samples do adsorb the dye molecules, but in varying quantities. Calcination at 900^∘C reduces the adsorption capacity of the ash to a great extent. Regression analysis shows that the experimental data fits both Langmuir and Freundlich isotherms for certain concentration limits. The adsorbate species are most probably transported from the bulk of the solution into the solid phase through intra-particle diffusion process. Kinetics of adsorption was found to follow pseudo second order rate equation with R ²∼ 0.99. The highest adsorption capacity (Q ₀) achieved is found to be ∼690 mg/g, which is even higher than the values reported for activated carbon from rice husk. The adsorption capacity of the ash samples are in good agreement with their surface area and pore volume.     

Sorption of phenol and radioactive cesium onto surfactant modified insolubilized humic acid

In this study, the sorption behavior of two important contaminants, phenol and radioactive cesium (¹³⁷Cs), onto surfactant modified insolubilized humic acid (SMIA) were investigated as a function of time, sorbate concentration utilizing the radiotracer method and UV–Vis spectroscopy. Phenol sorption process was well described by both Freundlich and Tempkin type isotherms, and cesium sorption was described by Freundlich and Dubinin–Radushkevich isotherms. It was found that SMIA adsorbs both cations and phenolic substances. Kinetic studies indicated that adsorption behavior of phenol obey the pseudo second order rate law. FTIR spectroscopic technique was used to understand the structural changes during modification process with surfactants.     

Nonlinear Analysis of the Kinetics and Equilibrium for Adsorptive Removal of Cd(II) by Starch Phosphate

In the present study, the nonlinear analysis method was used to evaluate the kinetics and equilibrium for Cd(II) adsorption on crosslinked starch phosphate (SP) from aqueous solution. The pseudo-first-order, pseudo-second-order and Elovich kinetic models were applied to test the kinetics experimental data, and the pseudo-first-order kinetic model provides a best correlation of the experimental data. Adsorption equilibrium data were fit by Langmuir, Freundlich, Dubinin-Radushkevich, and Sips isotherms. The results show that the data are best described by the Sips isotherms with a maximum adsorption capacity of 2.00 mmol/g. The effects of initial pH, and SP dose on the Cd(II) adsorption were also investigated. The adsorption capacities of Cd(II) on SP increase with the pH increasing from 2.0 to 8.0.     

Magnetic porous polymer microspheres: Synthesis,characterization and adsorption performance for the removal of phenol

The magnetic poly(ethylene glycol dimethacrylate-n-vinylimidazole) (Fe₃O₄@poly (EGDMA@VIM)) microspheres were prepared by suspension polymerization method using magnetite Fe₃O₄ nano-powder and the porosity, morphology, chemical composition and structure of the magnetic polymer microspheres were characterized. The specific surface area and swelling ratio of the Fe₃O₄@poly(EGDMA@VIM) microspheres were found to be 278.6?m²·g^–1 and 48%, respectively. The Fe₃O₄@poly(EGDMA@VIM) microspheres were used as an adsorbent for phenol removal. The effects of the parameters such as adsorbent dosage, temperature, pH and initial concentration of phenol solutions on the adsorption were investigated. The experimental adsorption equilibrium data obtained were fitted with Langmuir, Freundlich and Dubinin-Radushkevich isotherms and the pseudo-first-order, pseudo-second-order and intra–particle diffusion kinetic models. The adsorption equilibrium data agreed well with the Freundlich isotherm and the pseudo-second-order kinetic model. The maximum capacity of the Fe₃O₄@poly(EGDMA@VIM) microspheres was calculated to be 33.83?mg·g^–1 at 298?K and natural pH from Langmuir isotherm. The Fe₃O₄@poly(EGDMA@VIM) microspheres were found to be reusable for removal of phenol after desorption for several times. The result indicated that the Fe₃O₄@poly(EGDMA@VIM) microspheres are potential candidate for removal of phenol in wastewaters.     

Ultrasound-assisted derivatization of phenolic compounds in spiked water samples before pervaporation, gas chromatographic separation, and flame lonization detection

Summary A fully automated method, based on continuous ultrasound-assisted derivatization coupled with pervaporation before gas chromatographic separation and flame ionization detection, has been developed for the determination of phenol and cresols in water. Spiked water samples were doped with acetic anhydride and dipotassium hydrogen phosphate, before introduction into the flow system, to achieve catalytic acetylation of the target compounds. A multivariate study was performed to optimize the main factors affecting the derivatization process. The correlation coefficients, r, of the calibration plots obtained were better than 0.999 for cresols and better than 0.99 for phenol. Detection limits were 0.02 μg mL¹ for phenol, o-cresol, andp-cresol, and 0.05 μg mL¹ form-cresol. Reproducibility and repeatability, expressed as relative standard deviation, ranged from 2.0–3.9% and from 1.0–3.5% respectively.     

Equilibrium and kinetics study of Gd(III) and U(VI) adsorption from aqueous solutions by modified Sorrel’s cement

Modified Sorrel’s cement was prepared by the addition of ferric chloride. The modified cement (MF5) was analyzed and characterized by different methods. Adsorption of Gd(III) and U(VI) ions in carbonate solution has been studied separately as a function of pH, contact time, adsorbent weight, carbonate concentration, concentration of Gd(III) and U(VI) and temperature. From equilibrium data obtained, the values of Δ H, Δ S and Δ G were found to equal −30.9 kJ ⋅ mol⁻¹, −85.4 J ⋅ mol⁻¹ ⋅,K⁻¹, and −5.4 KJ ⋅ mol⁻¹, respectively, for Gd(III) and 18.9 kJ ⋅ mol⁻¹, 67.8 J ⋅ mol⁻¹ K⁻¹ and −1.3 KJ ⋅ mol⁻¹, respectively, for U(VI). The equilibrium data obtained have been found to fit both Langmuir and Freundlich adsorption isotherms. The batch kinetic of Gd(III) and U(VI) on modified Sorrel’s cement (MF5) with the thermodynamic parameters from carbonate solution were studied to explain the mechanistic aspects of the adsorption process. Several kinetic models were used to test the experimental rate data and to examine the controlling mechanism of the adsorption process. Various parameters such as effective diffusion coefficient and activation energy of activation were evaluated. The adsorption of Gd(III) and U(VI) on the MF5 adsorbent follows first-order reversible kinetics. The forward and backward constants for adsorption, k ₁and k ₂ have been calculated at different temperatures between 10 and 60^∘C. Form kinetic study, the values of Δ H ^* and Δ S ^* were calculated for Gd(III) and U(VI) at 25^∘C. It is found that Δ H ^* equals −14.8 kJmol⁻¹ and 7.2 kJmol⁻¹ for Gd(III) and U(VI), respectively, while Δ S ^* were found equal −95.7 Jmol⁻¹K⁻¹ and −70.5 Jmol⁻¹K⁻¹ for Gd(III) and U(VI), respectively. The study showed that the pore diffusion is the rate limiting for Gd(III) and (VI).     

Removal of Th(IV) ions from aqueous solution using bi-functionalized algae-yeast biosorbent

Composites could be more effective adsorbents than inorganic and organic components individually. In the present study, the red macro marine algae, Jania Rubens and yeast, Saccharomyces cerevisiae immobilized on silica gel were used as a constituent of bi-functionalized biosorbent to remove thorium ions from aqueous solution. Optimum biosorption conditions were determined as a function of pH, initial Th(IV) concentration, contact time, temperature, volume/mass ratio and co-ion effect. The morphological analysis of the biocomposite was performed by the scanning electron microscopy and functional groups in the biosorbent were determined by FT-IR spectroscopy. In order to find the adsorption characteristics, Langmuir, Freundlich, and Dubinin–Radushkevich adsorption isotherms were applied to the adsorption data. The data were well described by Langmuir adsorption isotherms while the fit of Freundlich adsorption isotherms and Dubinin–Radushkevich equation to adsorption data was poor. Using the equilibrium constant value obtained at different temperature, the thermodynamics properties of the biosorption (ΔG°, ΔH° and ΔS°) were also determined. The results show that biosorption of Th(IV) ions onto biocomposite was exothermic nature, spontaneous and more favorable at lower temperature under examined conditions.     

Comparative study of CTAB adsorption on bituminous coal and clay mineral

Adsorption of cetyltrimethylammonium bromide (CTAB) onto bituminous coal (BC) and a clay mineral, montmorillonite (MMT), was studied. Simultaneous measurements of the CTAB adsorption and zeta potential determination of the adsorption suspensions were carried out. The adsorption isotherms were found to be of the typical Langmuir type; values of the CTAB adsorption capacities were calculated (a _m = 0.65 mmol g⁻¹ for coal and a _m = 3.24 mmol g⁻¹ for MMT). The shape of the adsorption isotherms was correlated with zeta potential values at the adsorption equilibrium. The adsorption properties of both sorbents were studied by voltammetry on carbon paste electrodes (CPE) modified with coal-CTAB and MMT-CTAB system, respectively. Open circuit sorption with differential pulse voltammetry was performed in order to compare the sorption properties of the systems with the unmodified sorbents. The Cu²⁺ adsorption on BC and MMT decreased to approximately 50 % and 40 %, respectively. The surface adsorption mechanism of CTAB on coal based on hydrophilic interactions was proposed. In the case of montmorillonite, the CTAB intercalation is expected via ion exchange into the inter-layer space forming a double- or triple-layer arrangement.     

Nitrosation kinetics of phenolic components of foods and beverages

The kinetics of the reactions between sodium nitrite and phenol or m-, o-, or p-cresol in potassium hydrogen phthalate buffers of pH 2.5–5.7 were determined by integration of the monitored absorbance of the C-nitroso reaction products. At pH > 3, the dominant reaction was C-nitrosation through a mechanism that appears to consist of a diffusion-controlled attack on the nitrosatable substrate by NO⁺/NO₂H₂⁺ ions followed by a slow proton transfer step; the latter step is supported by the observation of basic catalysis by the buffer which does not form alternative nitrosating agents as nitrosyl compounds. The catalytic coefficients of both anionic forms of the buffer have been determined. The observed order of substrate reactivities (o-cresol ≈ m-cresol > phenol ≫ p-cresol) is explained by the hyperconjugative effect of the methyl group in o- and m-cresol, and by its blocking the para position in p-cresol. Analysis of a plot of ΔH^# against ΔS^# shows that the reaction with p-cresol differs from those with o- and m-cresol as regards the formation and decomposition of the transition state. The genotoxicity of nitrosatable phenols is compared with their reactivity with NO⁺/NO₂H₂⁺. © 1997 John Wiley & Sons, Inc.     

Adsorption of eicosane and 1,2-hexanediol from supercritical carbon dioxide on activated carbon and chromosorb

Supercritical adsorption isotherms were measured for eicosane and 1,2-hexanediol on activated carbon and chromosorb 101 at 324.2 K and 11.45 MPa. Adsorption isotherms of both solutes on activated carbon have typical shapes and can be modelled by Langmuir or Freundlich equations. For chromosorb 101 the equilibrium loadings are a linear function of the concentration of the solute in the fluid phase. These results suggest that for chromosorb 101 a partition of the solute between two immiscible phases rather than adsorption occurs.     

Adsorption of CO2 and N2 on synthesized NaY zeolite at high temperatures

NaY zeolite particles with a high surface area of 723 m²/g were synthesized by a hydrothermal method. Adsorption isotherms of pure gases CO₂ and N₂ on the synthesized NaY particles were measured at temperatures 303, 323, 348, 373, 398, 423, 448 and 473 K and pressures up to 100 kPa. It was found that the adsorption isotherm of CO₂ on the synthesized zeolite is higher than that on other porous media reported in the literature. All measured adsorption isotherms of CO₂ and N₂ were fitted to adsorption models Sips, Toth, and UNILAN in the measured temperature/pressure range and Henry’s law adsorption equilibrium constants were obtained for all three adsorption models. The adsorption isotherms measured in this work suggest that the NaY zeolite may be capable of capturing CO₂ from flue gas at high temperatures. In addition, isosteric heats of adsorption were calculated from these adsorption isotherms. It was found that temperature has little effect on N₂ adsorption, while it presents marked decrease for CO₂ with an increase of adsorbate loading, which suggests heterogeneous interactions between CO₂ and the zeolite cavity.     

Adsorption of selected herbicides from aqueous solutions on activated carbon

The adsorption of MCPA and 2,4-D on the activated carbon Filtrasorb 300 was studied. The adsorption isotherms of herbicides from aqueous solutions were measured over a wide range of solute concentrations and at different temperatures. The experimental equilibrium data were analyzed by the Langmuir–Freundlich isotherm taking into account the energetic heterogeneity of adsorption system. The effect of temperature and herbicide properties on its uptake was discussed. The thermal analysis was applied in order to find the differences in herbicide interactions with carbon surface. The kinetic dependences were measured and the relations between solute properties and adsorption rate were discussed.     

Flow injection-spectrophotometric determination of cresol compounds in water by reaction withp-aminophenol

A spectrophotometric method has been developed for the simultaneous determination ofo-cresol andm-cresol in water by reaction withp-aminophenol (PAP). Three different methodologies have been assayed; (i) batch analysis, after reaction in an alkaline medium in the presence of dissolved molecular oxygen as oxidizing agent, (ii) a stopped-flow procedure, carried out in the presence of KIO₄ and (iii) a flow injection method based on the same approach. The batch procedure requires 22 min for the full development of colour witho-cresol and 12 min form-cresol. In the stopped-flow mode, using KIO₄ and a reaction time of 12 min, better sensitivity can be obtained for both compounds and limits of detection of 10 g 1^–1 foro-cresol and 30 g 1^–1 form-cresol were found. The flow injection method has a lower sensitivity but permits more than 80 injections per hour. Based on the different maximum absorbance wavelengths obtained for the reaction products of PAP witho-cresol (614 nm) andm-cresol (632 nm), both compounds can be simultaneously determined in water samples and recoveries of 90 to 115% were found in spiked water samples of different types.     

Synthesis of nitrogen doped activated carbon/polyaniline material for CO2 adsorption

The equilibrium adsorption isotherms of carbon dioxide and nitrogen on the nitrogen doped activated carbon (NAC) prepared by the chemical activation of a pine cone‐based char/polyaniline composite were measured using a volumetric technique. CO₂ and N₂ adsorption experiments were done at three different temperatures (298, 308, and 318 K) and pressures up to 16 bar, and correlated with the Langmuir, Freundlich, and Sips models. The Sips isotherm model presented the best fit to the experimental data. The N‐doped adsorbent showed CO₂ and N₂ adsorption capacity of 3.96 mmol·g⁻¹ and 0.86 mmol·g⁻¹, respectively, at 298 K and 1 bar. The selectivity predicted by ideal adsorbed solution theory (IAST) model was achieved 47.17 for NAC at 1 bar and y_N2 = 0.85 which is a composition similar to flue gas. The results showed that NAC adsorbent has a high CO₂‐over‐N₂ selectivity in a binary mixture. The relatively fast sorption rate of CO₂ on NAC compared to N₂ indicates the stronger affinity between CO₂ and amine groups. The isosteric heat of adsorption of CO₂ by the NAC demonstrated the physico‐chemical adsorption of CO₂ on the adsorbent surface. These data showed that prepared NAC could be successfully applied in separation of CO₂ from N₂.     

Adsorption calorimetry

The efficiency of activated carbons prepared from corncob, to remove asphaltenes from toluene modeled solutions, has been studied in this work. The activating agent effect over carbonaceous solid preparation , and also temperature effect on the asphaltenes adsorption on the prepared activated carbons, was studied. The asphaltene adsorption isotherms were determined, and the experimental data were analyzed applying the Langmuir, Freundlich, Redlich–Peterson, Toth and Radke–Prausnitz and Sips models. Redlich–Peterson model described the asphaltenes isotherm on the activated carbons better. The asphaltenes adsorption capacities at 25° for activated carbons were: 1305 mg g^?1, 1654 mg g^?1 and 559.1 mg g^?1 for GACKOH, GACKP and GACH₃PO₄, respectively. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated from the adsorption isotherms in asphaltene solutions from toluene solutions, and it was found that the adsorption process was spontaneous and exothermic in nature. Kinetic parameters, reaction rate constant and equilibrium adsorption capacities were evaluated and correlated for each kinetic model. The results show that asphaltene adsorption is described by pseudo-second-order kinetics, suggesting that the adsorption process is chemisorption. The adsorption calorimetry was used to analyze the type of interaction between the asphaltenes and the activated carbons prepared in this work, and their values were compared with the enthalpic values obtained from the Clausius–Clapeyron equation.