Applications of Brazilian pine-fruit shell in natural and carbonized forms as adsorbents to removal of methylene blue from aqueous solutions--kinetic and equilibrium study

The Brazilian pine-fruit shell (Araucaria angustifolia) is a food residue, which was used in natural and carbonized forms, as low-cost adsorbents for the removal of methylene blue (MB) from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with sulfuric acid produced a non-activated carbonaceous material (C-PW). Both PW and C-PW were tested as low-cost adsorbents for the removal of MB from aqueous effluents. It was observed that C-PW leaded to a remarkable increase in the specific surface area, average porous volume, and average porous diameter of the adsorbent when compared to PW. The effects of shaking time, adsorbent dosage and pH on adsorption capacity were studied. In basic pH region (pH 8.5) the adsorption of MB was favorable. The contact time required to obtain the equilibrium was 6 and 4h at 25 degrees C, using PW and C-PW as adsorbents, respectively. Based on error function values (F(error)) the kinetic data were better fitted to fractionary-order kinetic model when compared to pseudo-first order, pseudo-second order, and chemisorption kinetic models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. For MB dye the equilibrium data were better fitted to the Sips isotherm model using PW and C-PW as adsorbents.     

Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from aqueous solutions

In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.     

Synthesis of some ferromagnetic composite resins and their metal removal characteristics in aqueous solutions

In this study, a procedure for synthesis of new organic-inorganic magnetic composite resins was established. The procedure was based upon immobilization of magnetite (Mag) as a ferromagnetic material within the polymer poly(acrylic acid acrylonitrile) P(AA-AN) and the ion exchange resin (Amberlite IR120). The produced magnetic resins, IR120-PAN-Mag (R1) and P(AA-AN)-Mag (R2) were assessed as sorbents for Cr(VI). Various factors influencing the sorption of Cr(VI), e.g., pH, equilibrium time, initial concentration and temperature were studied. The sorption process was very fast initially and maximum sorption was achieved within 3 h and pH 5.1. The kinetic of the system has been evaluated with pseudo first order model, second order model, Elovich model, intra-particle diffusion model and liquid film diffusion model. Chromium interaction with composite particles followed second-order kinetics with a correlation coefficient extremely high and closer to unity and rate constant (k_s) has the values 1.68 × 10⁻⁴ and 1.9 × 10⁻⁴ g (mg⁻¹ min⁻¹) for R1 and R2, respectively. The values of equilibrium sorption capacity (q_e) are consistent with the modeled data and attain the range 893–951 mg g⁻¹. Kinetically, both pore diffusion and film diffusion are participating in ruling the diffusion of Cr(VI) ions. The sorption data gave good fits with Temkin and Flory–Huggins isotherm models. The isotherm parameters related to the heat of sorption are in the range 8–16 kJ mol⁻¹ which is the range of bonding energy for ion exchange interactions and so suggest an ion exchange mechanism for removal of Cr(VI) by the composite sorbents. The adsorption process was exothermic with ΔH in the range of −73 to −97 kJ mol⁻¹. The negative values of Gibbs free energy confirm the feasibility and the spontaneous nature of Cr(VI) removal with these novel composites.     

Equilibrium, kinetic and thermodynamic study of the biosorption of uranium onto Cystoseria indica algae

Biosorption equilibrium, kinetics and thermodynamics of binding of uranium ions to Cystoseria indica were studied in a batch system with respect to temperature and initial metal ion concentration. Algae biomass exhibited the highest uranium uptake capacity at 15 °C at an initial uranium ion concentration of 500 mg l⁻¹ and an initial pH of 4. Biosorption capacity increased from 198 to 233 mg g⁻¹ with an decrease in temperature from 45 to 15 °C at this initial uranium concentration. The Langmuir isotherm model were applied to experimental equilibrium data of uranium biosorption depending on temperature. Equilibrium data fitted very well to the Langmuir model C. indica algae in the studied concentration range of Uranium ions at all the temperatures studied. The saturation type kinetic model was applied to experimental data at different temperatures changing from 15 to 45 °C to describe the batch biosorption kinetics assuming that the external mass transfer limitations in the system can be neglected and biosorption is chemical sorption controlled. The activation energy of biosorption (E_A) was determined as −6.15 using the Arrhenius equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of biosorption (ΔG°, ΔH° and ΔS°) were also evaluated.     

Removal of cadmium from aqueous solutions by adsorption onto orange waste

The use of orange wastes, generated in the orange juice industry, for removing cadmium from aqueous solutions has been investigated. The material was characterized by Fourier transform infrared spectroscopy and batch experiments were conducted to determine the adsorption capacity of the biomass. A strong dependence of the adsorption capacity on pH was observed, the capacity increasing as pH value rose. Kinetics and adsorption equilibrium were studied at different pH values (4-6). The adsorption process was quick and the equilibrium was attained within 3h. The maximum adsorption capacity of orange waste was found to be 0.40, 0.41 and 0.43 mmol/g at pH 4-6, respectively. The kinetic data were analysed using various kinetic models - pseudo-first order equation, pseudo-second order equation, Elovich equation and intraparticle diffusion equation - and the equilibrium data were tested using four isotherm models - Langmuir, Freundlich, Sips and Redlich-Peterson. The data were fitted by non-linear regression and five error analysis methods were used to evaluate the goodness of the fit. The Elovich equation provides the greatest accuracy for the kinetic data and the Sips model the closest fit for the equilibrium data.     

Cross-linked quaternary chitosan as an adsorbent for the removal of the reactive dye from aqueous solutions

Adsorption of reactive orange 16 by quaternary chitosan salt (QCS) was used as a model to demonstrate the removal of reactive dyes from textile effluents. The polymer was characterized by infrared (IR), energy dispersive X-ray spectrometry (EDXS) analyses and amount of quaternary ammonium groups. The adsorption experiments were conducted at different pH values and initial dye concentrations. Adsorption was shown to be independent of solution pH. Three kinetic adsorption models were tested: pseudo-first-order, pseudo-second-order and intraparticle diffusion. The experimental data best fitted the pseudo-second-order model, which provided a constant velocity, k₂, of 9.18 × 10⁻⁴ g mg⁻¹ min⁻¹ for a 500 mg L⁻¹ solution and a value of k₂, of 2.70 × 10⁻⁵ g mg⁻¹ min⁻¹ for a 1000 mg L⁻¹ solution. The adsorption rate was dependent on dye concentration at the surface of the adsorbent for each time period and on the amount of dye adsorbed. The Langmuir isotherm model provided the best fit to the equilibrium data in the concentration range investigated and from the isotherm linear equation, the maximum adsorption capacity determined was 1060 mg of reactive dye per gram of adsorbent, corresponding to 75% occupation of the adsorption sites. The results obtained demonstrate that the adsorbent material could be utilized to remove dyes from textile effluents independent of the pH of the aqueous medium.     

Study of Cu(II) biosorption by dried activated sludge: effect of physico-chemical environment and kinetics study

Biosorption is a recent technology used to remove heavy metal ions from aqueous solutions. The biosorption of copper ions from aqueous solution by dried activated sludge was investigated in batch systems. Effect of solution pH, initial metal concentration and particle size range were determined. The suitable pH and temperature for studied conditions were determined as 4.0 and 20 °C, respectively. The theoretical max biosorption capacity of activated sludge was 294 mg g⁻¹ at 20 °C for <0.063 mm particle size. The equilibrium data fitted very well to both Langmuir and Freundlich isotherm models. The pseudo first and second-order kinetic models were used to describe the kinetic data. The experimental data fitted to second-order kinetic model. The particle size and initial metal concentration were effected the biosorption capacity of dried activated sludge. An increase in the initial metal concentration increases of biosorption capacity, which also increases with decreasing particle size. Dried activated sludge has different functional groups according to the FT-IR results.     

Liquid-phase adsorption of phenols using activated carbons derived from agricultural waste material

Physical and chemical properties of activated carbons prepared from coconut shells (SAC and ATSAC) were studied. The adsorption equilibria and kinetics of phenol and 2,4-dichlorophenol from aqueous solutions on such carbons were then examined at three different temperatures (10, 25 and 40 °C). Adsorption of both phenol and 2,4-dichlorophenol increased with an increase in temperature. The experimental data were analyzed using the Langmuir and Freundlich isotherm models. Both the isotherm models adequately fit the adsorption data for both the phenols. The carbon developed through the acid treatment of coconut shells (ATSAC) exhibited relatively higher monolayer adsorption capacity for phenol (0.53 mmol g⁻¹) and 2,4-dichlorophenol (0.31 mmol g⁻¹) as compared to that developed by thermal activation (SAC) with adsorption capacity of 0.36 and 0.20 mmol g⁻¹, for phenol and 2,4-dichlorophenol, respectively. The equilibrium sorption and kinetics model parameters and thermodynamic functions were estimated and discussed. The thermodynamic parameters (free energy, enthalpy and entropy changes) exhibited the feasibility and spontaneous nature of the adsorption process. The sorption kinetics was studied using the pseudo-first-order and second-order kinetics models. The adsorption kinetics data for both the phenol and 2,4-dichlorophenol fitted better to the second-order model. An attempt was also made to identify the rate-limiting step involved in the adsorption process. Results of mass transfer analysis suggested the endothermic nature of the reaction and change in the mechanism with time and initial concentration of the adsorbate. The results of the study show that the activated carbons derived from coconut shells can be used as potential adsorbent for phenols in water/wastewater.     

Arsenic removal from an aqueous solution by modified A. niger biomass: batch kinetic and isotherm studies

Batch studies were conducted to examine the adsorption kinetics and adsorption capacity of iron oxide-coated biomass (IOCB) for As(III) and As(V). The optimum pH for As(V) and As(III) removal was found to be 6. The equilibrium time for removal of arsenic was found to be approximately 7 h. The adsorption of As(V) on IOCB was rapid compared to that of As(III) adsorption. An increase in temperature (from 5 to 30 °C) was found to increase As(III) removal, whereas in the case of As(V), the removal increased with temperature from 5 to 10 °C, but remained relatively constant thereafter up to 30 °C. The pseudo-second order rate equation was found to describe better the kinetics of arsenic adsorption than other equations. The isotherm data for As(V) removal fitted better with the Langmuir equation compared with other tested models and the isotherm data for As(III) removal fitted better with Redlich–Peterson equation than other tested models. Iron oxide-coated fungal biomass (A. niger) was found to be efficient in removing arsenic from an aqueous solution.     

Application of Brazilian pine-fruit shell as a biosorbent to removal of reactive red 194 textile dye from aqueous solution kinetics and equilibrium study

The Brazilian pine-fruit shell (Araucaria angustifolia) is a food residue, that was used as biosorbent for the removal of non-hydrolyzed reactive red 194 (NRR) and hydrolyzed reactive red 194 (HRR) forms from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with chromium (Cr-PW), with acid (A-PW), and with acid followed by chromium (Cr-A-PW) were also tested as alternative biosorbents for the removal of NRR and HRR from aqueous effluents. It was observed that the treatment of the Brazilian pine-fruit shell with chromium (Cr-PW and Cr-A-PW) leaded to a remarkable increase in the specific surface area and average porous volume of these biosorbents when compared to unmodified Brazilian pine-fruit shell (PW). The effects of shaking time, biosorbent dosage and pH on biosorption capacity were studied. In acidic pH region (pH 2.0) the biosorption of NRR and HRR were favorable. The contact time required to obtain the equilibrium was 24h at 25 degrees C. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. For NRR reactive dye the equilibrium data were best fitted to the Sips isotherm model using PW and A-PW as biosorbents, and Redlich-Peterson isotherm model using Cr-PW and Cr-A-PW as biosorbents. For HRR reactive dye the equilibrium data were best fitted to the Sips isotherm model using PW, A-PW and Cr-A-PW and the Redlich-Peterson isotherm model for Cr-PW as biosorbent.     

Adsorption and thermochemical data of divalent cations onto silica gel surface modified with humic acid at solid/liquid interface

Humic acid immobilized onto silica gel surface was studied by the calorimetric titration of divalent cations in aqueous solution. The adsorption isotherms were obtained by the batchwise method and were fitted to a modified Langmuir equation. The maximum number of moles per gram of the material gave: 10.42 ± 0.75, 13.16 ± 0.58, 7.87 ± 0.58 for copper, nickel and zinc, respectively. Gibbs free energies were negative for all systems and the adsorption interactions calorimetrically followed presented endothermic enthalpic values: 6.24 ± 0.47, 6.75 ± 0.74, 6.97 ± 0.58 kJ mol⁻¹ for the same sequence of divalent cations. All liquid/solid interface adsorptions were entropically driven.     

Assembly of extramembranous light-harvesting complexes of green sulfur photosynthetic bacterium Chlorobium tepidum on glass surface by electrostatic layer-by-layer adsorption

Extramembranous and peripheral light-harvesting complexes (chlorosomes) of green sulfur photosynthetic bacterium Chlorobium tepidum were electrostatically immobilized on a pyrex glass plate with the help of cationic polylysines. Absorbance of both Soret and Q_y bands of chlorosomes were linearly increased by repeated manipulation of layer-by-layer adsorption. Spectral features of chlorosome/polylysine layers on the glass plate indicate that the supramolecular structures of self-aggregates of bacteriochlorophyll(BChl)-c in chlorosomes are maintained on the solid surface. BChl-c molecules could be completely extracted from a single chlorosome/polylysine layer on a glass plate as monomers in acetone. Visible absorption spectra of extracted pigments indicate that BChl-c molecules inside chlorosomes were not denatured by electrostatic adsorption of chlorosomes and that the amount of BChl-c molecules in chlorosomes adsorbed on a glass plate was (1.3 ± 0.05) × 10^− 10 mol/cm² (mean ± standard deviation, three measurements). The estimation of BChl-c amounts suggests that chlorosomes are not so densely immobilized on a polylysine-adsorbed quartz plate.     

Comparative study of the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto S. cerevisiae: determination of biosorption heats

In this study, the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto inactive Saccharomyces cerevisiae was investigated as a function of initial pH, initial metal ion concentration and temperature. The Langmuir model was applied to experimental equilibrium data of Pb(II), Ni(II) and Cr(VI) biosorption depending on temperature and the maximum metal ions uptake at optimum biosorption temperature of 25 °C, were found to be 270.3, 46.3 and 32.6 mg g⁻¹, respectively. Using the Langmuir constant, b values obtained at different temperatures, the biosorption heats of Pb(II), Ni(II) and Cr(VI) were determined as −1.125, −1.912 and −2.89 kcal mol⁻¹, respectively. The results indicated that the biosorption of Pb(II), Ni(II) and Cr(VI) ions to S. cerevisiae is by the physical adsorption and has an exothermic nature.     

Error Anlaysis Studies of Dye Adsorption onto Activated Carbon from Aqueous Solutions

Adsorption of tartrazine and methylene blue from aqueous solution onto activated carbon has been investigated. Experimental datas obtained from dye adsorption have been studied by five two-parameter (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, and Frumkin), five three-parameter (Redlich-Peterson, Sips, Toth, Radke-Prausnitz, Koble-Corrigan) isotherm models. In this study, eight nonlinear error functions (sum squares errors, hybrid fractional error function, Marquardt's percent standard deviation, average relative error, sum of absolute error, the coefficient of determination, nonlinear chi-square test, and standard deviation of relative errors) were examined for isotherm equations. In order to clarify the adsorption kinetics fit of pseudo-first order and pseudo-second order kinetic models were used. The best fitting isotherm model was the Radke-Prausnitz and kinetics model was pseudo-second order for two dyes. Adsorption experiment showed that the maximum capacity of activated carbon's for methylene blue and tartrazine were 28.571 and 18.182 mg.g^?1, respectively.     

Effect of PWVA/Sb2O3 complex inhibitor on the corrosion behavior of carbon steel in 55%LiBr solution

The inhibition performance of PWVA/Sb₂O₃ complex inhibitor on carbon steel was studied in 55%LiBr + 0.07 mol L⁻¹ LiOH solution. Results indicated that the complex inhibitor decreased both anodic and cathodic polarization current density and widened the passive potential region of carbon steel in test solution and can be classified as mixed inhibitor. The complex inhibitor exhibited excellent inhibition performance on carbon steel when the concentrations of PWVA and Sb₂O₃ were 300 and 200 mg L⁻¹, respectively. With the solution temperature increasing from 145 to 240 °C, the corrosion rates of carbon steel increased from 4.71 to 120.66 μm y⁻¹. In solution containing the complex inhibitor, the relationship between relative coverage ratio of inhibitor on carbon steel surface and inhibition efficiency at 145 °C was obtained as the equation μ = 0.94η, it was a direct proportion. This result proved that the complex inhibitor inhibited the corrosion of carbon steel by geometric blocking effect. When solution temperature was 160 °C, the adsorption Gibbs free energy of PWVA and Sb₂O₃ on carbon steel were −49.59 and −44.29 kJ mol⁻¹, respectively. It indicated that the adsorption processes of PWVA and Sb₂O₃ on carbon steel surface were spontaneous processes. As a strong oxidant, PWVA facilitated the compact passive film comprising of FeO, Fe₂O₃ and Fe₃O₄ forming on the surface and itself was reduced to heteropoly blue. Sb₂O₃ adsorbed on carbon steel surface formed an adsorption film. PWVA and Sb₂O₃ behaved synergistic effect. The corrosion resistance performance of carbon steel in 55%LiBr + 0.07 mol L⁻¹ LiOH solution was improved by PWVA/Sb₂O₃ complex inhibitor.     

Grass waste: A novel sorbent for the removal of basic dye from aqueous solution

The aim of the present work was to investigate the feasibility of grass waste (GW) for methylene blue (MB) adsorption. The adsorption of MB on GW material was studied as a function of GW dose (0.05–1.20 g), solution pH 3–10, contact time and initial concentration (70–380 mg/L). The influence of these parameters on the adsorption capacity was studied using the batch process. The experimental data were analyzed by the Langmuir and Freundlich isotherms. The adsorption isotherm was found to follow the Langmuir model. The monolayer adsorption capacity was found to be 457.640 mg/g. The kinetic data were fitted to the pseudo-first-order and pseudo-second-order models, and were found to follow closely the pseudo-second-order kinetic model. The results revealed that GW adsorbent is potentially low-cost adsorbent for adsorption of MB.     

Deep levels in GaInAs grown by molecular beam epitaxy and their concentration reduction with annealing treatment

X-ray diffraction (XRD), current–voltage (IV), capacitance–voltage (CV), deep-level transient Fourier spectroscopy (DLTFS) and isothermal transient spectroscopy (ITS) techniques are used to investigate the thermal annealing behaviour of three deep levels in Ga_0.986In_0.014As heavily doped with Si (6.8 × 10¹⁷ cm⁻³) grown by molecular beam epitaxy (MBE). The thermal annealing was performed at 625 °C, 650 °C, 675 °C, 700 °C and 750 °C for 5 min. XRD study shows good structural quality of the samples and yields an In composition of 1.4%. Two main electron traps are detected by DLTFS and ITS around 280 K, with activation energies of 0.58 eV and 0.57 eV, capture cross sections of 9 × 10⁻¹⁵ cm² and 8.6 × 10⁻¹⁴ cm² and densities of 2.8 × 10¹⁶ cm⁻³ and 9.6 × 10¹⁵ cm⁻³, respectively. They appear overlapped and as a single peak, which divides into two smaller peaks after annealing at 625 °C for 5 min.

Annealing at higher temperatures further reduces the trap concentrations. A secondary electron trap is found at 150 K with an activation energy of 0.274 eV, a capture cross section of 8.64 × 10⁻¹⁵ cm² and a density of 1.38 × 10¹⁵ cm⁻³. The concentration of this trap level is also decreased by thermal annealing.     

Equilibrium modeling and kinetic studies on the adsorption of basic dye by a low-cost adsorbent: coconut (Cocos nucifera) bunch waste

In this paper, the ability of coconut bunch waste (CBW), an agricultural waste available in large quantity in Malaysia, to remove basic dye (methylene blue) from aqueous solution by adsorption was studied. Batch mode experiments were conducted at 30 degrees C to study the effects of pH and initial concentration of methylene blue (MB). Equilibrium adsorption isotherms and kinetics were investigated. The experimental data were analyzed by the Langmuir, Freundlich and Temkin models of adsorption. The adsorption isotherm data were fitted well to Langmuir isotherm and the monolayer adsorption capacity was found to be 70.92 mg/g at 30 degrees C. The kinetic data obtained at different concentrations have been analyzed using a pseudo-first-order, pseudo-second-order equation and intraparticle diffusion equation. The experimental data fitted very well the pseudo-second-order kinetic model.     

Competitive adsorption of Cu (II), Co (II) and Ni (II) from their binary and tertiary aqueous solutions using chitosan-coated perlite beads as biosorbent

A new composite chitosan-coated biosorbent was prepared and was used for the removal and recovery of heavy metals from aqueous solution. In the present investigation, equilibrium adsorption characteristics of Cu (II), Ni (II), and Co (II) from their binary and tertiary solution on newly developed biosorbent chitosan-coated perlite beads were evaluated through batch and column studies. These beads were characterized by using FTIR, EDXRF and surface area analysis techniques. The effect of various biosorption parameters like effect of pH, agitation time, concentration of adsorbate and amount of adsorbent on extent of adsorption was investigated. The adsorption follows Lagergren first order kinetic model. The equilibrium adsorption data were fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters were evaluated. Both the models represent the experimental data satisfactorily. The sorbent loaded with metal was regenerated with 0.1N NaOH solution. Furthermore the column dynamic studies indicate the re-usage of the biosorbent.