Equilibrium,kinetics and thermodynamics of hexavalent chromium biosorption on pristine and zinc chloride activated Senna siamea seed pods

Hexavalent chromium contamination in water is an issue of huge concern due to its use at a high scale, toxicity and non-biodegradability. Biosorption is a cost effective and unconventional strategy for the elimination of Cr(VI). Here, a novel biosorbent Senna siamea seed pod biomass and its chemically activated form have been investigated for the elimination of hexavalent chromium from aqueous solution. The biosorbent was characterized by using BET, FTIR, FESEM-EDX and TGA techniques. Parameters controlling the biosorption process were optimized as pH 2.0, temperature 30°C, initial Cr(VI) concentration 500?mg/L, biosorbent dose 0.5?g/L. Optimized contact time was 210 and 180 min for pristine biomass and activated carbon, respectively. Langmuir isotherm correlated well with experimental data revealing that the biosorption occurred in monolayer pattern. Maximum biosorption capacity calculated by Langmuir biosorption isotherm was 119.18 and 139.86?mg/g for S. siamea pristine biomass and activated carbon, respectively. Pseudo-second order kinetic model correlated well with experimental data. Thermodynamic studies suggested that the biosorption process occurs in a non-spontaneous, stable and endothermic manner. These interesting findings on Cr(VI) biosorption by S. siamea seed pod biomass and S. siamea zinc chloride activated carbon vouches for its potential application as an unconventional biosorbent.     

Removal of toxic chromium(VI) from aqueous solution by activated carbon using Casuarina equisetifolia

Highly activated carbon from the seed husk of Casuarina Casuarinas equisetifolia, a worldwide famous plant, have been prepared and tested for the removal of toxic Cr(VI) from its aqueous solution. The adsorbent was investigated for influences of initial chromium concentration (75, 100, 125, and 150 mg l^-1), pH, contact time, and quantity of carbon on removal of Cr(VI) from aqueous solution at room temperature (25±2 °C). The adsorption kinetic of Cr(VI) was studied, and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R²≥0.99). The Langmuir and Freundlich models fit the isotherm data well. Furthermore, the Gibbs free energy was obtained for each system and was found to be-5.29 kJ mol^-1 for removal of Cr(IV). The negative value of Δ G° indicates the feasibility and spontaneous nature of adsorption. The results indicate that acidic pH (1.05) supported the adsorption of Cr(IV) on activated carbon. The maximum adsorption capacity of Cr(VI) on activated carbon was about 172.4 mg g^-1 at pH 1.05.     

Biosorption potential of Cr(VI) by Kocuria sp. ASB107, a radio-resistant bacterium isolated from Ramsar,Iran

Heavy metal pollution in soil and wastewater is a worldwide environmental issue in which microorganisms play a significant role for its removal. In the present study, biosorption of Cr(VI) by the live and dead cells of Kocuria sp. ASB107, a radio-resistant bacterium, was investigated. The effect of contact time, solution pH, initial hexavalent chromium concentration and adsorbent dose on biosorption efficiency was studied. Also, live cells were further immobilised on various matrices by different techniques and then were examined for tolerance to chromium biosorption. Experimental results indicated that the removal efficiency of chromium increased with decrease in pH, initial Cr(VI) concentration, and also increase in adsorbent dose and the contact time. The maximum removal efficiency of live and dead cells at acidic pH of 4–4.5, contact time of 24 hours, adsorbent dose 1.6?g/100?mL and initial chromium concentration 25?mg/L were 82.4% and 69.2%, respectively. The adsorption data was described well by Langmuir isotherm model. Among all immobilisation techniques tested, cross-linking showed the highest biosorption of Cr(VI). Results indicated that live cells of Kocuria sp. ASB107 were better than dead ones.     

Adsorptive features of banana (Musa paradisiaca) stalk-based activated carbon for malachite green dye removal

Chemically prepared activated carbon derived from banana stalk (BSAC) was used as an adsorbent to remove malachite green (MG) dye from aqueous solution. BSAC was characterised using thermogravimetric analyser, Brunauer Emmett Teller, Fourier transform infrared spectrometry, scanning electron microscopy, pH_pzc, elemental analysis and Boehm titration. The effectiveness of BSAC in adsorbing MG dye was studied as a function of pH, contact time, temperature, initial dye concentration and repeated desorption–adsorption processes. pH_pzc of BSAC was 4.5 and maximum dye adsorption occurred at pH 8.0. The rate of dye adsorption by BSAC was very fast initially, attaining equilibrium within 120 min following a pseudo-second-order kinetic model. Experimental data were analysed by Langmuir, Freundlich and Dubinin–Raduschevich isotherms. Equilibrium data fitted best into the Langmuir model, with a maximum adsorption capacity of 141.76 mg·g^?1. Δ G ⁰ values were negative, indicating that the process of MG dye adsorption onto BSAC was spontaneous. The positive values of Δ H ⁰ and Δ S ⁰ suggests that the process of dye adsorption was endothermic. The regeneration efficiency of spent BSAC was studied using 0.5 M HCl, and was found to be in the range of 90.22–95.16% after four cycles. This adsorbent was found to be both effective and viable for the removal of MG dye from aqueous solution.     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Biosorption of lead and cadmium using marine algae

The use of algae (Ulva fasciata, green and Sargassum sp., brown) to reduce lead and cadmium levels from mono-metal solutions was investigated. The brown algae showed higher efficiency for the accumulation of lead (～1.5 times) and cadmium (～2 times) than green algae. The optimum pH value is found to be between 4 and 5.5. Regarding biomass concentration, an increase in metals percentage removal and a decrease in metal uptake capacity coincided with the increase in biomass concentration. All light metals (Ca, Mg and Na) showed a suppressive effect on biosorption capacity. The enhancement of biosorption in the case of NaOH was obvious. The biosorption process (65–90%) occurred within 3?min. Experimental data were in high agreement with the pseudo-second-order kinetic model and Freundlich model for lead and cadmium biosorption using different biosorbents. In the desorption study, 0.2?mol?L^?1 HCl recorded the best concentration for the elution of metals from the biomass. The biosorption capacity decreased over the four operational cycles for both lead and cadmium. Infrared analysis showed that amino, hydroxyl and carboxyl functional groups provide the major biosorption sites for metal binding. Use of the above-mentioned algae for cheap metal absorbance is considered as one water treatment criterion.     

Removal of Novacron Golden Yellow dye from aqueous solutions by low-cost agricultural waste: Batch and fixed bed study

The present work describes the removal of Novacron Golden Yellow (NGY) dye from aqueous solutions using peanut hulls. The experiments were performed with native, pretreated and immobilised forms of peanut hulls. The effect of various operational parameters (pH, biosorbent dose, initial dye concentration and temperature etc.) was explored during batch study. NGY showed maximum removal at low pH and low biosorbent dose. High initial dye concentration facilitated the biosorption process. Maximum dye removal with native, pretreated and immobilised biomass was found to be 35.7, 36.4 and 15.02 mg/g respectively. The experimental data were subjected to different kinetic and equilibrium models. The kinetic data confirmed the fitness of pseudo-second-order rate law for NGY biosorption. The equilibrium modelling was carried out by Freundlich, Langmuir and Temkin models. The isothermal data of NGY removal were best described by Freundlich adsorption isotherm. Negative values of Free energy change (Δ G⁰) for NGY with native and pretreated biomass depicted the spontaneous nature of biosorption process. In column mode, the effects of bed height, flow rate and initial dye concentrations were optimised. Maximum NGY biosorption (7.28 mg/g) was observed with high bed height, low flow rate and high initial concentration in continuous mode. Bohart–Adams model best fitted to the data obtained from column studies. The results indicated that the peanut hulls could be used effectively for the removal of dyes containing wastewater.     

Pomegranate husk as an adsorbent in the removal of toxic chromium from wastewater

The use of a new sorbent developed from the husk of pomegranate, a famous fruit in Egypt, for the removal of toxic chromium from aqueous solution has been investigated. The batch experiment was conducted to determine the adsorption capacity of the pomegranate husk. The effects of initial metal concentration (25 and 50 mg l^?1), pH, contact time, and sorbent concentration (2–6 g l^?1) have been studied at room temperature. A strong dependence of the adsorption capacity on pH was observed, the capacity increased as the pH decreased, and the optimum pH value was pH 1.0. Adsorption equilibrium and kinetics were studied with different sorbent and metal concentrations. The adsorption process was fast, and equilibrium was reached within 3 h. The maximum removal was 100% for 25 mg l^?1 of Cr⁶⁺ concentration on 5 g l^?1 pomegranate husk concentration, and the maximum adsorption capacity was 10.59 mg g^?1. The kinetic data were analysed using various kinetic models—pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion equations—and the equilibrium data were tested using several isotherm models, Langmuir, Freundlich, Tempkin, Dubinin–Radushkevich, and Generalized isotherm equations. The Elovich and pseudo-second-order equations provided the greatest accuracy for the kinetic data, while Langmuir and Generalized isotherm models were the closest fit for the equilibrium data. The activation energy of sorption has also been evaluated as 0.236 and 0.707 kJ mol^?1 for 25 and 50 mg l^?1 chromium concentration, respectively.     

Brown marine algae turbinaria conoides as biosorbent for Malachite green removal: Equilibrium and kinetic modeling

In this study, the biosorption of Malachite green (MG) onto Turbinaria conoides, brown marine algae, was studied with respect to initial pH, temperature, initial dye concentration, and sorbent dosage. The optimum initial pH and temperature values for MG removal were found to be 8.0 and 30°C, respectively. Sorbent dosage was found to strongly influence the removal of MG. Equilibrium studies were carried out to test the validity of the Langmuir (q _max = 66.6 mg/g and b = 0.526 mL mol/L) and the Freundlich (n = 1.826 and K = 3.751 mg/g) isotherms. The kinetic studies indicated the validity of the pseudo first-order and second-order equation.     

1,3,5-triazine-triethylenetetramine polymer: an efficient adsorbent for removal of Cr(VI) ions from aqueous solution

The synthesis of 1,3,5-triazine-triethylenetetramine (TATETA), its characterization by infrared spectroscopy and elemental analysis, and its application for removal of Cr(VI) ions from aqueous solution is reported. The effects of pH, contact time, initial concentration of Cr(VI), sorbent dose, and temperature on adsorption were investigated and optimized by batch adsorption experiments. Adsorption was highest at acidic conditions with an equilibration time of 25 min. The adsorption followed a Langmuir model, with an adsorption capacity of 303 mg g^?1, was second order in its kinetics, and exothermic and thus spontaneous.     

Preparation and characterization of <Emphasis Type="Italic">β</Emphasis>-FeOOH-coated sand and its adsorption of Cr(VI) from aqueous solutions

Batch adsorption experiments were conducted to explore the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand. We investigated the key factors which affected the adsorption process such as adsorbent dosage, initial pH, initial Cr(VI) ion concentration, contact time and temperature. The uptake of Cr(VI) was very rapid and 44.3%, 51.6%, 58.9% of the adsorption happened during the first 180 minutes at 293K, 303K and 313K, respectively. The pseudo-second-order rate equation successfully described the adsorption kinetics. To study the adsorption isotherm, two equilibrium models, the Langmuir and Freundlich isotherms, were adopted. At 293K, 303K and 313K, the adsorption capacities obtained from the Langmuir isotherm were 0.060, 0.070 and 0.076 mg Cr(VI) per gram of the adsorbent, respectively. Thermodynamic parameters such as the change of energy, enthalpy and entropy were calculated using the equilibrium constants. The negative value of ΔG ⁰ and the positive value of ΔH ⁰ showed that the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand was spontaneous, endothermic and occurred by physisorption.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

Biosorption of Cr(VI) from wastewater using Sorghastrum Nutans L. Nash

Sorghastrum Nutans L. Nash is used as an adsorbent for the removal of Cr(VI) from wastewater. Adsorption coupled reduction i.e. indirect reduction is the mechanism of Cr(VI) removal by the biomaterial. The adsorbent surface became highly positively charged at lower pH, adsorption rate of Cr(VI) is faster and reduction reaction also accelerates at lower pH since the binding of negatively charged Cr(VI) ion species to the cationic groups is enhanced and protons take part in this reaction. The adsorbent is characterised by using XRD, FTIR, SEM and EDAX analysis. OH bending, CN stretching/bending and NH stretching play a major role in Chromium adsorption. Experimental values follow pseudo-second order reaction and Langmuir adsorption isotherm. Surface diffusion is the rate controlling mechanism for the process. The maximum percentage of Cr(VI) removal obtained is 75.5% with 7?g/L dosage at pH 1.3 and adsorbate concentration was 100?mg/L. From the normal probability, residual, contour, 3D surface, main effect and interaction plot along with t-test, ANOVA, and F-test, it is observed that pH has the most significant effect on the percentage removal followed by adsorbent dosage and time. The adsorbate concentration has the least effects and interaction effects are found to be significant.     

Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium,kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔG^o (−0.8– −4.58 kJ·mol⁻¹), ΔH^o (15.6–44.4 kJ·mol⁻¹), and ΔS^o (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr(III) concentration. The analysis of the values of biosorption activation energy (E_a = −7 kJ·mol⁻¹) and the intra-particle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Investigation of acetaminophen adsorption with a biosorbent as a purification method of aqueous solution

ABSTRACT

Pharmaceutical compounds are considered emerging environmental pollutants that have a potential harmful impact on environment and human health. In this study, the spiky green horse-chestnut shell was used for the biosorption and removal of acetaminophen from aqueous solution. It was analysed how the parameters, like contact time, pH, mass of biosorbent and temperature, influence the effectiveness of acetaminophen removal from aqueous solutions. The equilibrium was quickly achieved after 10?min (～60%). The amount of acetaminophen adsorption slightly increased with the increase of the mass of biosorbent, and for example for an aqueous solution containing 10?mg/L of acetaminophen adsorption was increased from 62% to 81%. The promising results obtained at pH ranged between 2 and 9, which shows that the adsorption of acetaminophen did not depend on the pH and it may be a consequence of the predominant microporous sorbent and its surface charge. The result is better correlated to a pseudo-second-order kinetic model of type 2 (r ²?=?0.9992) than pseudo-first-order. A sorption mechanism of acetaminophen on biosorbent was also proposed. The sorption of acetaminophen over biosorbent is mainly preceded by hydrophilic interactions between hydroxyl and carbonyl groups in pharmaceutical molecules and hydroxyl and carboxyl groups on the surface of biosorbent.     

Chromium (VI) biosorption by immobilized Aspergillus niger in continuous flow system with special reference to FTIR analysis

Aspergillus niger was treated with acid and immobilized in calcium alginate matrix. The dynamic removal of Cr (VI) ion was studied using continuously fed column packed with immobilized biosorbent beads. Column experiments were carried out to study the effect of various bed heights (20, 30, 40 cm) under different flow rates (5, 7.5, 10 ml min(-1)) on efficiency of biosorption. The maximum time (1020 minutes; 17 hr) before breakthrough point was observed in case of 40 cm bed height with flow rate of 5ml min(-1). FTIR analysis of acid treated immobilized A. niger was used fora qualitative and preliminary analysis of chemical functional groups present on its cell wall which provided the information on nature of cell wall and Cr (VI) interaction during the process of biosorption. The IR spectra of biosorbent recorded before and after chromium biosorption had shown some changes in the band patterns, which were finally analyzed and was found that chemical interaction such as ion-exchange between carboxyl (-COOH), hydroxyl (-OH) and amine (-NH2) group of biosorbent and Chromium ion were mainlyinvolved in biosorption of Cr (VI) onto A. niger cell wall surface. The biosorbed metal was eluted from biosorbent by using 0.1 M H2SO4 as eluant. Immobilized biosorbent could be reused for five consecutive biosorption and desorption cycles without apparent loss of efficiency after its reconditioning. Considering all above factors together this paper discusses the efficient chromium biosorption process carried out by immobilized A. niger biosorbent.     

Cr (VI) and Fe (III) removal using Cajanus cajan husk

Husk of tur dal (Cajanus cajan) was investigated as a new biosorbent for the removal of Fe (III) and Cr (VI) ions from aqueous solutions. Parameters like agitation time, adsorbent dosage and pH were studied at different initial Fe (III) and Cr (VI) concentrations. The biosorptive capacity of the Tur dal husk was dependent on the pH of the chromium and iron solution, with pH 2 and 2.5 respectively being optimal. The adsorption data fit well with Langmuir and Freundlich isotherm models. The practical limiting adsorption capacity (qmax) calculated from the Langmuir isotherm was 96.05 mg of Cr(VI)/ g of the biosorbent at an initial pH of 2.0 and 66.65 mg/g at pH 2.5. The infrared spectra of the biomass revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Cr (VI) and Fe (III) ions. Characterisation of tur dal husk has revealed that it is an excellent material for treating wastewaters containing low concentration of metal ions.     

Biosorption of cadmium and nickel ions using marine macrophyte,Cymodocea nodosa

ABSTRACT

Seagrass (Cymodocea nodosa) ability to remove cadmium and nickel ions from single metal solutions was investigated in the present study. Metal ions were measured in the solution using an atomic absorption spectrophotometer. Various operational parameters (initial pH, biomass dose, metal ion concentration, and contact time) were tested and found to affect the uptake capacity of Cd (II) and Ni (II). More than 70% of biosorption capacity occurred in the first few minutes for both metal ions. The pseudo-second-order kinetic model and the Langmuir model were found to best fit the experimental data of Cd (II) and Ni (II) biosorption. The maximum uptake capacity (q_max) was 11.6 and 16.7?mg.g^?1 for Cd (II) and Ni (II), respectively. The biosorbent was characterised using Fourier transform infrared spectrometry (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDX). The infrared spectrum demonstrated that hydroxyl, carboxyl, and phenolic functional groups are the major binding sites for Cd (II) and Ni (II) metals. The ion exchange mechanism plays an important role during biosorption process as shown in EDX analysis. Our results conclude that marine macrophyte C. nodosa can be used as a low-cost biosorbent for the removal of Cd (II) and Ni (II) in wastewater.     

Adsorptive removal of Drimarine Red HF-3D dye from aqueous solution using low-cost agricultural waste: batch and column study

This study involves the utilisation of peanut husk for the removal of Drimarine Red HF-3D dye from aqueous solutions. Batch study experiments were conducted with native, HNO₃-treated and Na-alginate-immobilised peanut husk biomass. Maximum dye removal (95.24 mg/g) was obtained with HNO₃-treated biomass. The experimental data were successfully explained with a pseudo-second-order kinetic model for all types of biosorbents. The equilibrium data fitted well to the Freundlich adsorption isotherm model. A thermodynamic study was also carried out to check the nature of the adsorption process. A fixed-bed column study for Drimarine Red HF-3D was carried out to optimise the effect of bed height, flow rate and initial dye concentration using peanut husk biomass. The column study showed that biosorption capacity increased with the increase in initial dye concentration and bed height, but decreased with increased flow rate. Data for Drimarine Red HF-3D were in very good agreement with the bed depth service time model. Fourier transform infrared analysis demonstrated the involvement of different functional groups in dye biosorption. These results showed that peanut husk biomass possessed good potential for the removal of Drimarine Red HF-3D from aqueous solution.     

Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.