Equilibrium and a two-stage batch adsorber design for reactive or disperse dye removal to minimize adsorbent amount

The adsorption of a reactive dye (Reactive Yellow K-4G) and a disperse dye (Disperse yellow brown S-2RFL) onto polyepicholorohydrin-dimethylamine (EPIDMA) cationic polymer modified bentonite (EPIDMA-bentonite) in batch adsorber was studied, respectively. Two equilibrium models, the Langmuir and Freundlich models were selected to follow the adsorption process. It was shown that the equilibrium experimental data for reactive dye adsorption could be well described by the Freundlich model, but for disperse dye the Langmuir model could be better. Based on the well correlated adsorption isotherm, an adsorption process design model was developed for the design of a two-stage batch adsorber to predict the minimum amount of adsorbent to achieve a specified percentage of dye removal at a given volume of wastewater effluents. The adsorption process design analysis indicated that compared with the single-stage batch adsorption, the two-stage process could significantly save adsorbent to meet the higher demands of dye removal efficiency.     

Adsorption kinetics of a basic dye from aqueous solutions onto apricot stone activated carbon

The preparation of activated carbon from apricot stone with H₂SO₄ activation and its ability to remove a basic dye, astrazon yellow 7GL, from aqueous solutions were reported in this study. The adsorbent was characterized by FTIR, BET and SEM, respectively. The effects of various experimental parameters, such as initial dye concentration, pH, adsorbent dosage and temperature were investigated in a batch-adsorption technique. The optimum conditions for removal of the basic dye were found to be pH 10, 6 g/l of adsorbent dosage and equilibrium time of 35 min, respectively. A comparison of three kinetic models, the pseudo first-order, second-order and diffusion controlled kinetic models, on the basic dye-adsorbent system showed that the removal rate was heavily dependent on diffusion controlled kinetic models. The adsorption isotherm data were fitted well to Langmuir and Freundlich isotherms. The adsorption capacity was calculated as 221.23 mg/g at 50 °C. Thermodynamics parameters were also evaluated. The values of enthalpy and entropy were 49.87 kJ/mol and 31.93 J/mol K, respectively, indicating that this process was spontaneous and endothermic. The experimental studies were indicated that ASC had the potential to act as an alternative adsorbent to remove the basic dye from aqueous solutions.     

Determination of cation exchange capacity of woody plant roots using ammonium acetate extractant

Summary A rapid exchange procedure using ammonium acetate as an extractant was developed for measurement of cation exchange capacity (CEC) of plant roots. The CEC values obtained with 1∶100 and 1∶200 root/solution ratios were almost equal, though the values increased with length of the time of immersion in both the root/solution ratios. The method gave higher CEC values with fresh roots as compared to dried roots. However, dried milled and dried unmilled roots gave identical values.     

Adsorption of BSA on strongly basic chitosan: Equilibria

Equilibrium isotherms for adsorption of bovine serum albumin (BSA) on a new adsorbent, a strongly basic crosslinked chitosan (Chitopearl 2503), which is hard and is not compressed by pressure in a column, have been presented and compared with diethylaminoethyl (DEAE) Sepharose Fast Flow (hard gel). In Chitopearl 2503, when only buffer existed in the BSA solution, the isotherm was not affected by the initial concentration of BSA but it was affected by pH considerably. The isotherm was favorable when pH >/= pl ( congruent with 4.8). When NaCl existed in the BSA solution, the amount of BSA absorbed on the resin decreased with increasing concentration of NaCl. When the concentration of NaCl was 200 mol/m(3), the resin did not adsorb BSA at all. The equilibrium data were correlated by the Langmuir equation reasonably well. The BSA may be adsorbed mainly by electrostatic attraction between negatively charged BSA and positively charged quanternary ammonium groups at pH > pl and by protonation reaction of the primary ammonium groups by weak acid groups of BSA at pH = pl. These are confirmed by measuring the amount of inorganic ion exchanged for BSA. In DEAE Sepharose Fast Flow, the isotherm was favorable when pH > pl but unfavorable ar pH = pl. The saturation capacity of BSA on Chitopearl 2503 is about 1.3 to 2.2 times larger than that on DEAE Sepharose Fast Flow. (c) 1994 John Wiley & Sons, Inc.     

Biosorption of phosphate from synthetic wastewater by biosolids

The aim of this study was to determine the potential of phosphate (P) removal from wastewater by biosolids prepared by the immobilization of P-accumulating bacteria onto organic bentonite. Organic bentonite was prepared by treating bentonite clay with quaternary ammonium salt — cetyltrimetylammonium (CTA) bromide. Cation exchange capacity (CEC) of the bentonite was found to be 179.0 meq/100 g of the dry bentonite. The CTA occupied ca. 175% of the CEC. Modification of bentonite with CTA in amounts higher than 55% of the CEC resulted in the change of zeta potential of particles from negative to positive. Only in reactors containing organic bentonite samples occupied with 3.5 and 28% of the CEC was P efficiently removed from wastewater by combined adsorption and bacterial uptake in the biomass. Organic bentonite samples with higher CTA loadings (from 55 to 175% of the CEC) showed bactericidal effects. To enhance P removal from wastewater in the aerated biological system, biosolids consisting of P-accumulating bacteria and organic bentonite can be used, but special attention should be given to the configuration of sorbed CTA molecules and its potential desorption.     

Adsorptive transfer stripping voltammetry: Determination of nanogram quantities of DNA immobilized at the electrode surface

In adsorptive transfer stripping voltammetry (AdTSV), DNA is first adsorbed at the electrode, the electrode is washed and transferred (with the adsorbed layer) in the medium not containing DNA, and voltammetric analysis is performed in this medium. Adsorption can be performed from a drop of DNA solution, which makes it possible to reduce the volume of the analyzed sample by two orders of magnitude as compared to that of conventional voltammetry. With the hanging mercury drop electrode the limit of detection of single-stranded DNA is below 0.1 micrograms/ml; thus if the adsorption is performed from a 10-microliter drop of DNA solution subnanogram quantities of single-stranded DNA are sufficient for the analysis. In AdTSV the behavior of single- and double-stranded DNAs markedly differ from each other in a manner similar to that in the conventional voltammetric or polarographic analysis; AdTSV can thus be used in DNA structure analysis. In AdTSV the DNA transport and its adsorption at the electrode are separated from the electrode process; due to this fact it is possible (a) to perform the voltammetric analysis of DNA from media not suitable for voltammetric analysis of the conventional type, (b) to study the interaction of immobilized DNA with other substances in solution without the results of the voltammetric analysis being influenced by DNA interactions in the bulk of solution, and (c) to exploit the differences of adsorbability of DNA and other substances in order to separate them on the electrode.     

In vitro evaluation of the capacity of zeolite and bentonite to adsorb aflatoxin B1 in simulated gastrointestinal fluids

Anin vitro study using single concentration and isotherm adsorption was carried out to evaluate the capacity of Vietnamese produced zeolite and bentonite to adsorb aflatoxin B₁ (AFB₁) in simulated gastrointestinal fluids (SGFs), and a commercial sorbent hydrated sodium calcium aluminosilicate (HSCAS) was used as reference. In this study, AFB₁ solution was mixed with sorbents (0.3, 0.4 and 0.5% w/v) in SGFs at pH 3 and pH 7 and shaken for 8 h, centrifuged and the supernatant measured by Vicam fluorometer. Adsorption of AFB₁ onto zeolite and bentonite varied according to the pH of SGFs and was lower than HSCAS. Linearity between the increased amount of AFB₁ adsorbed on sorbents and the decrease of sorbent concentration was observed for bentonite and HSCAS, except for zeolite in SGFs at pH 7. The observed maximum amounts of AFB₁ adsorbed on bentonite and HSCAS were 1.54 and 1.56 mg/g, respectively. The adsorption capacities of bentonite and HSCAS for AFB₁ were 12.7 and 13.1 mg/g, respectively, from fitting the data to the Freundlich isotherm equation. Improvement in processing and purification for bentonite is needed to enhance the surface area, which would probably result in better adsorptive capacity for this sorbent.     

Isolation of L-theanine from tea solution by cation exchange resin in batch and fixed bed column

L-Theanine, a bioactive compound in tea, was isolated from tea solution using cation exchange resin no.732. The adsorption of L-theanine by cation exchange resin no.732 fit the Langmuir isotherm model and was a monolayer molecular interaction process. Thermodynamic studies revealed that the adsorption of L-theanine by resin no.732 was an exothermic and spontaneous physically driven process. The adsorption capacity was influenced by temperature, initial concentration, and pH. The L-theanine adsorption capacity under conditions at room temperature, pH 4.73, and initial L-theanine concentration 18 g/L was 241.731 ± 3.679 mg/g. The Thomas model was fit to describe the column adsorption data at different flow rates and initial concentrations. The L-theanine adsorbed by resin no.732 could be desorbed by 0.134 mol/L Na₂HPO₄ aqueous solution with a recovery rate of 84.96%. These findings indicate that resin no.732 was a promising material for isolating L-theanine from tea solution.     

Adsorption of BSA on QAE-dextran: equilibria

Equilibrium isotherms for adsorption of bovine serum albumin (BSA) on a strong-base (QAE) dextran-type ion exchanger have been determined experimentally. They were not affected by the initial concentration of BSA but were affected by pH considerably. They were correlated by the Langmuir equation when pH >/= 5.05 and by the Freundlich equation of pH 4.8, which is close to pl approximately 4.8 of BSA. The contribution of ion exchange to adsorption of BSA on the ion exchanger was determined experimentally. The maximum amounts of inorganic anion exchanged for BSA were 1% and 0.4% of the exchange capacity of the ion exchanger at pH 6.9, respectively. Since the effect of the ion exchange on the adsorption appeared small, BSA may be adsorbed mainly by electrostatic attraction when pH >/= 5.05 and by hydrophobic interaction or hydrogen bonding at pH 4.8. When NaCl coexisted in the solution, the shape of the isotherm was similar to the Langmuir isotherm, but it is shifted to the right. When the concentration of NaCl was 0.2 mol/dm(3), BsA was not adsorbed on the resin. When BSA was dissolved in pure water, the saturation capacity of BSA on HPO(4) (2-),-orm resin was about 2 times larger than that for adsorption from the solution with buffer (pH 6.9 and 8.79). The saturation capacity for adsorption of BSA in pure water on HPO(4) (2-) + H(2)O(4) (-)-from resin was much smaller than that from the solution with buffer. The isotherms for univalent Cl(-)-and H(2)PO(4) (-)-form resin was peculiar; that is, the amount of BSA adsorbed decreased with increasing the liquid-phase equilibrium concentration of BSA. (c) 1993 John Wiley & Sons, Inc.     

Adsorption of cationic dye from aqueous solutions by date pits: Equilibrium,kinetic, thermodynamic studies,and batch adsorber design

The retention profile of methylene blue from aqueous solutions onto the solid adsorbent date pits has been investigated in a batch system. The characterization and adsorption efficiency for methylene blue was evaluated using date pits. Fourier Transform Infra-Red, Scanning Electron Microscope, Brunauer–Emmett–Teller analysis were performed to determine the characteristics of the material. The effect of contact time, initial dye concentration, adsorbent dosage, temperature, and solution pH were investigated. The adsorption was found to increase with increasing time, decreasing concentration of dye, decreasing temperature and increasing dosage up to equilibrium values which was 20 min, 25°C, and 0.1 g adsorbent, respectively. The adsorption was favorable at high and low pH (pH 3, pH 7). The adsorption equilibrium data were best fitted by Freundlich isotherm. The adsorption kinetics was found to follow the pseudo second order kinetic model. Thermodynamic parameters such as free energy, enthalpy, and entropy were calculated and found to be ?4.6 kJ/mole, ?7.9 kJ/mole, and ?11.8 kJ/mole, respectively. The thermodynamic parameters of the uptake of methylene blue onto the date pits indicated that, the process is exothermic and proceeds spontaneously at low temperature. A single stage batch adsorber was designed for adsorption of methylene blue by Date Pits based on optimum isotherm.     

Mechanism of ammonium adsorption from wastewater by modified bentonite and optimization by response surface

Three modified bentonites, dry alkali modification, thermal modification, and acid modification, were prepared and characterized by XRD and FTIR. Batch experiments were performed to evaluate their efficiency as adsorbent for ammonium removal. Multi-variables interaction effects were evaluated by Response Surface Methodology. The results showed that the adsorption efficiency of ammonium by dry alkali modification bentonite was the best in three modified methods; the next was that of thermal modification. The crystalline structure of bentonite was significantly changed with dry alkali modification. Na₂SiO₃ and Na₂AlSi₃O₈(OH) were achieved by bentonite with powder NaOH modification. The increase in the mole ratio of exchangeable cations indicated that the adsorption efficiency of ammonium increased; while the layer spacing of bentonite expanded with the amount of the adsorbed water and hydrated water increased by thermal modification. In multi-variables interaction effects (holding time, calcination temperature, pH, dosage), the most significant factors were calcination temperature and dosage.     

The distribution of ammonium ion from a localized source into the soil

The distribution of ammoniun ions from a concentrated source in the soil is calculated with a computed model based on chromatographic theory. The analytical solution for the chromatographic equation with convective transport in a pistonlike flow, for a non linear adsorption isotherm, is compared with computer simulation model results and actual experimental data from soil solumns.Adsorption isotherms for the exchange of Ca⁺⁺ by NH₄ ⁺ ions in the range of 0.01 to 6 eq NH₄/I were obtained. The isotherm are described by a modification of Freundlich's isotherm.Ammonium displacement is a frontal movement. The resulting concentration profile is a uniform zone of influence within which ammonium concentration is close to 2/3 of the soil C.E.C. A relatively narrow transition zone exists between the zone of influence and the bulk soil.Good correlation was obtained between experimental and computed ammonium concentration distribution along the soil profile after leaching.The results presented in this work indicate that a quantitative estimation of the extent to which ammonium ions are transported from application site, and the processes following this transport, can be obtained.Present address of the first author: Universidad Catolica de Chile, Dept. of Soils, Chile.     

One-pot synthesis and characterization of cross-linked quaternized chitosan microspheres as protein adsorbent

The one-pot synthesis and characterization of cross-linked quaternized chitosan microspheres (CQCM) as a protein adsorbent are presented. First of all, chitosan particles were prepared by spray drying method, and then they were quaternized and cross-linked in turn with glycidyltrimethylammonium (GTMAC) chloride and glutaraldehyde in isopropanol containing 10% water in one-pot. The effect of the reaction temperature, reaction time and the amounts of added GTMAC and glutaraldehyde on the protein adsorption ability of CQCM was investigated. The adsorption behavior of the CQCM prepared in the optimum synthetic conditions was well described by the Langmuir isotherm with maximum adsorption capacity equal to 1424 mg BSA/g dry weight. The particle size ranged from 7.6 to 48.9 μm. The mechanism of adsorption-desorption of BSA to the CQCM was ion-exchange. Finally, the extraction of soybean peroxidase from crude soybean peroxidase solution using the CQCM was performed.     

A sustainable process for adsorptive removal of methylene blue onto a food grade mucilage: kinetics,thermodynamics, and equilibrium evaluation

Abstract

Adsorption of dyes onto natural materials like polysaccharides is considered a green chemistry approach for remediation of wastewater. In this work, the polysaccharide isolated from the corm of Colocasia esculenta (L.) Schott or taro tuber (CEM) was utilized for removing methylene blue (MB) from aqueous solution by batch adsorption method. The CEM adsorbent was characterized by FTIR spectroscopy, Brunauer–Emmett–Teller (BET), and scanning electron microscopy (SEM). The solution pH and adsorbent dose have been found to have a significant positive correlation with the adsorptive removal efficiency of CEM for MB dye. The removal efficiency of CEM was found to be 72.35% under the optimum conditions; 20?mg/L initial concentration of dye, 120?mg of adsorbent dose, solution pH 8.5, 311.2?K temperature and 80?min contact time. The adsorption of MB onto CEM followed best the Freundlich isotherm and pseudo-second-order kinetics. The adsorption was thermodynamically favorable and was endothermic in nature. The desorption/adsorption data justifiably indicated the reuse capability of CEM adsorbent for MB adsorption. Hence, CEM may be regarded as an eco-friendly and cost-effective natural adsorbent for MB dye removal from aqueous solution.     

Interaction between collagen and adenosine 5'-triphosphate.

A quantitative study was made of the adsorption of adenosine 5′-triphosphate (ATP) on collagen by following the change in the absorbance at 258 nm of ATP in the soaking solution. The amount of ATP adsorbed decreased exponentially with the increase of pH up to pH 8 and fell off more rapidly at higher pH values. At a given pH, when the concentration of ATP was increased, the amount of ATP adsorbed increased following the pattern of a Langmuir isotherm. The adsorption was independent of the cation present. The adsorption of adenosine 5′-diphosphate was essentially the same as that for ATP. For tendons deposited with calcium phosphate, the amount of ATP adsorbed decreased compared to natural tendons. The adsorption of ATP on collagen fibers inhibited the contraction caused by calcium chloride, calcium bromide, and lithium bromide. In solution, ATP had very little effect on the denaturation of acid-soluble collagen caused by calcium chloride.     

Chromium in plants

Chromium is an essential trace element and is associated with some biological pathways, especially with glucose tolerance. For these reasons, we decided to determine the concentration of chromium in two sets of Brazilian medicinal plants. The first group consisted of plants that are considered as antidiabetic, whereas the second included plants that do not have this therapeutic property. The concentration of chromium was determined by flameless atomic absorption. All the plants analyzed contain chromium in the normal range for this element, but the hypoglycemic plants contain more chromium than the others (1–4 μg/g compared to 0.5–1.5 μg/g).     

Synthesis,micellisation and interaction of novel quaternary ammonium compounds derived from l-Phenylalanine with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine as model membrane in relation to their antibacterial activity,and their selectivity over human red blood cells

A series of quaternary ammonium compounds (QUATS) derived from l-Phenylalanine have been synthesized and their antibacterial efficiencies were determined against various strains of Gram-positive and Gram-negative bacteria. The antibacterial activity increased with increasing chain length, exhibiting a cut-off effect at C₁₄ for Gram-positive and C₁₂ for Gram-negative bacteria. The l-Phenylalanine QUATS displayed enhanced antibacterial properties with a higher cut-off point compared to their corresponding l-Phenylalanine ester hydrochlorides. The CMC was correlated with the MIC, inferring that micellar activity contributes to the cut-off effect in antibacterial activity. The hemolytic activities (HC₅₀) of the QUATS against human red blood cells were also determined to illustrate the selectivity of these QUATS for bacterial over mammalian cells. In general, the MIC was lower than the HC₅₀, and assessment of the micellar contribution to the antibacterial and hemolytic evaluation in TBS as a common medium confirmed that these QUATS can act as antibacterial, yet non-toxic molecules at their monomer concentrations. The interaction of the QUATS with the phospholipid vesicles (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC) in the presence of 1-anilino-8-naphthalene sulfonate (ANS) and 1,6-diphenyl-1,3,5-hexatriene (DPH) as fluorescence probes showed that the presence of the quaternary ammonium moiety causes an increase in hydrophobic interactions, thus causing an increase in antibacterial activity.     

Spent Rooibos (Aspalathus linearis) Tea Biomass as an Adsorbent for Organic Dye Removal

Spent rooibos (Aspalathus linearis) tea biomass can be used as an inexpensive biosorbent for xenobiotic removal. Seventeen dyes have been tested for their affinity to spent rooibos tea biomass. Eight dyes were used to study the adsorption process in detail. The dye adsorption has been described with the Langmuir isotherm. The calculated maximum adsorption capacities reached the value of over 200 mg of dye per gram of dried rooibos biomass for Bismarck brown Y. Spent rooibos tea biomass was also magnetically modified by contact with microwave-synthesized magnetic iron oxide nano- and microparticles. This new type of magnetically responsive biocomposite material can be easily separated by means of strong permanent magnets. Both native and magnetically modified spent rooibos biomass have shown excellent adsorption capacities for various types of organic dyes, so they are highly promising adsorbents in environmental technologies for selected xenobiotic removal.     

Synthesis and anticoagulant activity of the quaternary ammonium chitosan sulfates

Quaternary ammonium chitosan sulfates with diverse degrees of substitution (DS) ascribed to sulfate groups between 0.52 and 1.55 were synthesized by reacting quaternary ammonium chitosan with an uncommon sulfating agent (N(SO₃Na)₃) that was prepared from sodium bisulfite (NaHSO₃) through reaction with sodium nitrite (NaNO₂) in the aqueous system homogeneous. The structures of the derivatives were characterized by FTIR, ¹H NMR and ¹³C NMR. The factors affecting DS of quaternary ammonium chitosan sulfates which included the molar ratio of NaNO₂ to quaternary ammonium chitosan, sulfated temperature, sulfated time and pH of sulfated reaction solution were investigated in detail. Its anticoagulation activity in vitro was determined by an activated partial thromboplastin time (APTT) assay, a thrombin time (TT) assay and a prothrombin time (PT) assay. Results of anticoagulation assays showed quaternary ammonium chitosan sulfates significantly prolonged APTT and TT, but not PT, and demonstrated that the introduction of sulfate groups into the quaternary ammonium chitosan structure improved its anticoagulant activity obviously. The study showed its anticoagulant properties strongly depended on its DS, concentration and molecular weight.     

Inactivation of clay-associated bacteriophage MS-2 by chlorine.

The model system consisted of bacteriophage MS-2, bentonite clay, and hypochlorous acid (HOC1). Factors that influenced association of the bacterial virus with bentonite were the titer of unadsorbed viruses, clay concentration, cation concentration, temperature, stirring rate, and the presence of soluble organics. Variation of the kinetic adsorption rate constant with stirring speed indicates that phage attachment is a diffusion-limited process; the attachment reaction has an apparent activation energy of 1 kcal/mol. About 18% of clay-associated bacteriophages was recovered by mixing the suspension with an organic eluent. Inactivation data were obtained from batch reactors operated under those conditions in which loss of HOC1 was minimal during the reaction. Bacteriophages attached to clay were more resistant to HOC1 than were freely suspended phages; for equivalent HOC1 concentrations, clay-associated phages required about twice the time that freely suspended phages required for loss of 99% of the initial virus titer.