Magnetic chitosan nanoparticles for removal of Cr(VI) from aqueous solution

A simple method was introduced to prepare magnetic chitosan nanoparticles by co-precipitation via epichlorohydrin cross-linking reaction. The average size of magnetic chitosan nanoparticles is estimated at ca. 30 nm. It was found that the adsorption of Cr(VI) was highly pH-dependent and its kinetics follows the pseudo-second-order model. Maximum adsorption capacity (at pH 3, room temperature) was calculated as 55.80 mg·g^? 1, according to Langmuir isotherm model. The nanoparticles were thoroughly characterized before and after Cr(VI) adsorption. From this result, it can be suggested that magnetic chitosan nanoparticles could serve as a promising adsorbent for Cr(VI) in wastewater treatment technology.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide

A type of ZrO₂·nH₂O was synthesized and its Cr(VI) removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The Cr(VI) adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model. The adsorption capacity increased from 61 to 66 mg g^?1 when the temperature was increased from 298 to 338 K. The positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid–liquid interface during the adsorption. ΔG° values obtained were negative indicating a spontaneous adsorption process. The effective desorption of Cr(VI) on ZrO₂·nH₂O could be achieved using distilled water at pH 12.     

Adsorption of Cr(VI) from aqueous solutions by spent activated clay

Adsorption of Cr(VI) onto spent activated clay (SAC), a waste produced from an edible oil refinery company, was investigated for its beneficial use in wastewater treatment. After pressure steam treatment, SAC was used as an adsorbent. The adsorption kinetic data were analyzed and fitted well in a pseudo-first-order equation and the rate of removal was found to speed up with decreasing pH and increasing temperature. Activation energy for the adsorption process was found to be 4.01–5.47 kcal/K mol. The Langmuir adsorption isotherm was used to fit the equilibrium data and the effect of pH, temperature and ionic strength were studied. The maximum adsorption capacities for Cr(VI) ranged from 0.743 to 1.422 mg/g for temperature between 4 and 40 °C under a condition of pH 2.0. The studies conducted show the process of Cr(VI) removal to be spontaneous at high temperature and endothermic in nature. From the waste utilization and environment point of view, the work carried out is important and useful. Results obtained can serve as baseline data for designing a treatment process using this low-cost adsorbent for the treatment of wastewater rich in Cr(VI).     

Cr(VI) reduction in aqueous solutions by siderite

Hexavalent chromium is a common and toxic pollutant in soils and wastewaters. Reduction of the mobile Cr(VI) to less mobile and less toxic Cr(III) is a solution for decontamination of industrial effluents. In this study, the reduction of hexavalent chromium in aqueous solutions by siderite was investigated. The influences of amount of acid, contact time, siderite dosage, initial Cr(VI) concentration, temperature and particle size of siderite have been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The amount of acid is the most effective parameter affecting the Cr(VI) reduction since carbonaceous gangue minerals consume acid by side reactions. The highest Cr(VI) reduction efficiency (100%) occurred in the 50 mg/l Cr(VI) solution containing two times acid with respect to stoichiometric amount of Cr(VI) and at the conditions of siderite dosage 20 g/l, contact time 120 min and temperature 25 degrees C. Reduction efficiency increased with increase in temperature and decrease in particle size. The reduction capacity of siderite was found to be 17 mg-Cr(VI)/g.     

Mathematical models applied to the Cr(III) and Cr(VI) breakthrough curves

Trivalent and hexavalent chromium continuous biosorption was studied using residual brewer Saccharomyces cerevisiae immobilized in volcanic rock. The columns used in the process had a diameter of 4.5 cm and a length of 140 cm, working at an inlet flow rate of 15 mL/min. Breakthrough curves were used to study the yeast biosorption behavior in the process. The saturation time (ts) was 21 and 45 h for Cr(III) and Cr(VI), respectively, and a breakthrough time (tb) of 4 h for Cr(III) and 5 h for Cr(VI). The uptake capacity of the biosorbent for Cr(III) and Cr(VI) were 48 and 60 mg/g, respectively. Two non-diffusional mathematical models with parameters t0 and sigma were used to adjust the experimental data obtained. Microsoft Excel tools were used for the mathematical solution of the two parameters used.     

Biosorption of Cr (VI) from aqueous solutions by biomass of Agaricus bisporus

In this study, biosorption of Cr (VI) ion was investigated by using biomass of Agaricus bisporus (a species of mushroom) in a temperature and shaking speed controlled shaker. The effect of shaking speed, biomass concentration, initial metal ion concentration and initial pH on biosorption yield was determined and the fitness of biosorption data for Freundlich and Langmuir adsorption models was investigated. Optimum biosorption conditions were found to be pH 1, C0=50 mg/l, m=10 g/l, shaking speed=150 rpm, T=20 degrees C Cr (VI), respectively. It was found that biosorption of Cr (VI) ions onto biomass of A. bisporus was better suitable to Freundlich adsorption model than Langmuir adsorption model. The correlation coefficients for the second-order kinetic model obtained were found to be 0.999 for all concentrations. These indicate that the biosorption system studied belongs to the second-order kinetic model.     

Characteristics of cellulosic amine-crosslinked copolymer and its sorption properties for Cr(VI) from aqueous solutions

A new cellulosic amine-crosslinked copolymer was prepared after the amination reaction with cotton stalk peel (CSP). The physicochemical characteristics of amine-crosslinked cotton stalk peel (AC-CSP) and raw CSP were determined after the surface analysis (including specific surface area, micropore volume and SEM), zeta potential analysis and spectrum analysis (FTIR and Raman spectrum). The sorption properties of AC-CSP for Cr(VI) were evaluated in the static, column sorption and desorption tests. The surface characteristics indicated the absence of porous adsorption in the potential Cr(VI) sorption mechanism. Zeta potential and spectrum analysis of AC-CSP illustrated the involvement of amine groups in the Cr(VI) sorption process. The sorption capacity of AC-CSP for Cr(VI) was 129.0mg/g as comparison with 14.8 mg/g of raw CSP. Flow rate and influent Cr(VI) concentration were demonstrated as two influencial factors in the column sorption tests. NaCl was used as the eluent, and the desorption efficiencies during three successive cycles were 75.9%, 69.8% and 64.3%, respectively. In addition, the results of the static, column sorption and desorption tests illustrated the complicated interactions between Cr(VI) and AC-CSP including complexation and ion exchange mechanisms.     

Effective removal and fixation of Cr(VI) from aqueous solution with Friedel's salt

Friedel's salt (3CaO·Al₂O₃·CaCl₂·10H₂O or Ca₄Al₂(OH)₁₂Cl₂(H₂O)₄) is a calcium aluminate hydrate formed by hydrating cement or concrete in seawater at a low cost. In the current study, we carefully examined the adsorption behaviors of Friedel's salt for Cr(VI) from aqueous solution at different concentrations and various initial pHs. The adsorption kinetic data are well fitted with the pseudo-first-order Lageren equation at the initial Cr(VI) concentration from 0.10 to 8.00 mM. Both the experimental and modeled data indicate that Friedel's salt can adsorb a large amount of Cr(VI) (up to 1.4 mmol Cr(VI)/g) very quickly (t_1/2 = 2–3 min) with a very high efficiency (>99% Cr(VI) removal at [Cr] < 4.00 mM with 4.00 g/L of adsorbent) in the pH range of 4–10. In particular, the competitive adsorption tests show that the Cr(VI) removal efficiency is only slightly affected by the co-existence of Cl⁻ and HCO₃⁻. The Cr(VI)-fixation stability tests show that only less than 0.2% adsorbed Cr(VI) is leaching out in water at pH 4–10 for 24 h because the adsorption/exchange of Cr(VI) with Friedel's salt leads to the formation of a new stable phase (3CaO·Al₂O₃·CaCrO₄·10H₂O). This research thus suggests that Friedel's salt is a potential cost-effective adsorbent for Cr(VI) removal in wastewater treatment.     

Removal of Cr(VI) from aqueous solutions using agricultural waste 'maize bran'

Novel biosorbent 'maize bran' has been successfully utilized for the removal of Cr(VI) from aqueous solution. The effect of different parameters such as contact time, sorbate concentration, pH of the medium and temperature were investigated and maximum uptake of Cr(VI) was 312.52 (mgg(-1)) at pH 2.0, initial Cr(VI) concentration of 200mgL(-1) and temperature of 40 degrees C. Effect of pH showed that maize bran was not only removing Cr(VI) from aqueous solution but also reducing toxic Cr(VI) into less toxic Cr(III). The sorption kinetics was tested with first order reversible, pseudo-first order and pseudo-second order reaction and it was found that Cr(VI) uptake process followed the pseudo-second order rate expression. Mass transfer of Cr(VI) from bulk to the solid phase (maize bran) was studied at different temperatures. Different thermodynamic parameters, viz., DeltaG degrees , DeltaH degrees and DeltaS degrees have also been evaluated and it has been found that the sorption was feasible, spontaneous and endothermic in nature. The Langmuir and Freundlich equations for describing sorption equilibrium were applied and it was found that the process was well described by Langmuir isotherm. Desorption studies was also carried out and found that complete desorption of Cr(VI) took place at pH of 9.5.     

Removal of Cr(VI) from aqueous solutions using modified red pine sawdust

The adsorption of Cr(VI) from aqueous solutions on sawdust (SD), base extracted sawdust (BESD) and tartaric acid modified sawdust (TASD) of Turkish red pine tree (Pinus nigra), a timber industry waste, was studied at varying Cr(VI) concentrations, adsorbent dose, modifier concentration and pH. Batch adsorption studies have been carried out. Sawdust was collected from waste timber industry and modified with various amount of tartaric acid (TA) (0.1-1.5M). The batch sorption kinetics has been tested and the applicability of the Langmuir and Freundlich adsorption isotherms for the present system has been tested at 25+/-2 degrees C. Under observed test conditions, the equilibrium adsorption data fits the linear Freundlich isotherms. An initial pH of 3.0 was most favorable for Cr(VI) removal by all adsorbents. Maximum Cr(VI) was sequestered from the solution within 120 min after the beginning for every experiment. The experimental result inferred that chelation and ion exchange is one of the major adsorption mechanisms for binding metal ions to the SD. Percentage removal of Cr(VI) was maximum at the initial pH of 3.0 (87.7, 70.6 and 55.2% by TASD, BESD, and SD, respectively). Adsorption capacities range from 8.3 to 22.6 mg/g for SD samples.     

Removal of Cr(VI) and As(V) from aqueous solutions by HDTMA-modified zeolite Y

The synthesized zeolite NaY from rice husk ash (RHA) and the commercial zeolite NaY both modified with surfactants in amounts equal to 50%, 100% and 200% of their external cation exchange capacity (ECEC) were used to remove chromate and arsenate anions from aqueous solutions. While the unmodified zeolite Y had little or no affinity for the Cr(VI) and As(V) anionic species, the surfactant-modified zeolite Y (SMZY) showed significant ability to remove of these anions from the aqueous solutions. The highest chromates and arsenates adsorption efficiency was observed from solutions of pH values 3 and 8, respectively because of the dominance of the univalent species of both anions. The adsorption equilibrium data were best fitted with the Langmuir isotherm model with the highest removal capacities observed for the SMZY initially prepared considering the hexadecyltrimethyl ammonium (HDTMA) amount equal to the 100% of the ECEC of zeolite Y. Synthesized SMZY remove Cr(VI) and As(V) more than the corresponding commercial one due to its lower silica to alumina ratio. Thus, the HDTMA-covered modified zeolite Y synthesized using RHA can be used to remove Cr(VI) and As(V) from water.     

Oxidation of Cr(III) in tannery sludge to Cr(VI): field observations and theoretical assessment

Sludge, soil and leachate samples collected from a chromium-contaminated tannery waste dumping site in Kanpur, India, were found to contain considerable amounts of Cr(VI), despite the fresh tannery sludge containing little or no Cr(VI). Literature reports suggested that dry Cr(III) precipitates could be converted to Cr(VI) when heated in the presence of oxygen. Also, Cr(III) in aqueous phase could be oxidized through interaction with manganese dioxide (MnO2) surface to Cr(VI). Measurement of manganese in the sludge samples collected from the site showed concentrations up to 0.6 mg/g. Based on equilibrium calculations, it was determined that both dry phase Cr(III) oxidation by atmospheric oxygen and aqueous phase Cr(III) oxidation by MnO2 surface were thermodynamically feasible. It was further suggested that in aqueous phase, manganese may act effectively as an electron transporter between Cr(III) and dissolved oxygen during Cr(III) oxidation, leading to regeneration of MnO2 solid phase. Further, as dissolved Cr(III) is oxidized, dissolution of Cr(OH3) will take place to maintain the equilibrium between the dissolved and solid phases of Cr(III). In the pH range of 3-10, and at oxygen partial pressure (P(O2)) of 10(-6) atm or higher, equilibrium conditions stipulate nearly complete conversion of Cr(III) to Cr(VI). At P(O2) of 10(-20) atm or lower, very little Cr(VI) is expected to be present under equilibrium conditions. In the intermediate P(O2) regions, incomplete dissolution of the Cr(OH3) solid phase and only partial conversion of chromium from +3 to the +6 oxidation state is expected, especially at lower pH values.     

Cr(VI) removal from aqueous solution using chemically reduced and functionalized graphene oxide

Chemically reduced and functionalized graphene oxide (GO) was prepared by refluxing of GO with ethylenediamine (ED) using dimethyl formamide (DMF) as solvent. It was confirmed that both ED and DMF contributed to the reduction and functionalization of GO. The resulting adsorbent (ED–DMF–RGO) with amine groups was highly efficient in removing Cr(VI) from its aqueous solution and could be easily separated by filtration. The optimum pH for total Cr removal was observed at pH 2.0 and the Cr(VI) removal capacity of ED–DMF–RGO at this pH was 92.15 mg g^?1, which was about 27 times higher than that of activated carbon, even nearly 4–8 times higher than that of various modified activated carbons. The presence of other ions such as Na⁺, K⁺, Ca²⁺, Cl^?, and Br^? had little effect on the removal of Cr(VI). Interestingly, Cr(VI) was reduced to low-toxic Cr(III) during the adsorption process, which followed an indirect reduction mechanism. Both the Cr(VI) adsorption and subsequent reduction of adsorbed Cr(VI) to Cr(III) contributed to the Cr(VI) removal. The obtained ED–DMF–RGO may be applicable in Cr(VI) removal if they are produced on a large scale and at low price in near future.     

Removal of As(V) and Cr(VI) from aqueous solutions using solid waste from leather industry

This study evaluated the feasibility of using a solid waste from the leather industry as an adsorbent for removal of Cr(VI) and As(V) from aqueous media. The adsorbent material was characterized by chemical analyses, infrared spectroscopy, and scanning electronic microscopy (SEM) prior to reaction in order to assess its surface properties. Langmuir and Freundlich equations were used for analyzing the experimental data, which showed a better fit to the Langmuir model, thus suggesting a monolayer adsorption process in the surface of the adsorbent. The high amounts of Cr(VI)-133 mg g(-1) and As(V)-26 mg g(-1) adsorbed demonstrates the great potential for using this solid waste from the leather industry as a low-cost alternative to the traditionally used adsorbent materials.     

Removal of Cr(VI) from aqueous solutions by low-cost biosorbents: marine macroalgae and agricultural by-products

In this study, adsorption of Cr(VI) onto the four low-cost biosorbents (Laminaria japonica, P. yezoensis Ueda, rice bran and wheat bran) was investigated depending on solution pH, contact time, adsorbent concentration and adsorption isotherms by employing batch adsorption technique. The adsorption capacities were significantly influenced by solution pH, with lower pH favoring higher Cr(VI) removal for various biosorbents. The ionic strength of NaCl was also observed to have a significant impact on the Cr(VI) adsorption due to the competition of Cl(-) in the aqueous solutions. The batch equilibrium data were correlated to Langmuir and Freundlich isotherms and the data fitted better to the Freundlich isotherm equation. The apparent thermodynamic parameters were calculated for each of the four biosorbents and the obtained numerical values showed that the Cr(VI) adsorption onto the various low-cost biosorbents is spontaneous, entropy-driven and endothermic processes. The batch kinetic data were correlated to the pseudo-first order and pseudo-second order models and the data fitted better to the pseudo-second order equation. An intraparticle diffusion model was applied to investigate the adsorption mechanisms. The adsorption capacities for various biosorbents studied in this work were inversely proportional to the adsorbent concentrations.     

Adsorption of Pb(II) and Cr(III) from aqueous solution on Celtek clay

This paper presents the adsorption of Pb(II) and Cr(III) from aqueous solution on Celtek clay. Batch experiments were carried out as a function of the adsorbent dosage, solution pH, shaking time, and temperature. The equilibrium data of fitted well with the linear Langmuir and Freundlich models. Dubinin-Radushkevick (D-R) isotherm model was applied to describe the nature of the adsorption of the metals, and found that it occurred physically. Thermodynamic parameters, the change in Gibbs free energy change (DeltaG degrees), enthalpy (DeltaH degrees) and entropy (DeltaS degrees) were also calculated. These parameters indicated that the adsorption of Pb(II) and Cr(III) on Celtek clay was feasible, spontaneous and exothermic process in nature. Based on the results, it was concluded that Celtek clay had a significant potential for removing Pb(II) and Cr(III) from wastewater using adsorption method.     

Enhancing the electrochemical Cr(VI) reduction in aqueous solution

In this study we present the cathodic Cr(VI) reduction using electrodissolution of iron anode. In batch experiments we tested four different cathodic materials; the best conditions were found when copper was used. It is observed that when more current is applied into the electrochemical cell faster reduction rates are achieved. Continuous experiments also reveal that Cr(VI) reduction could be done in a very efficient way. To confirm the experimental data, cyclic voltammetry was used and it was found that the cathodic Cr(VI) reduction is taking place.     

Cr(VI) adsorption on functionalized amorphous and mesoporous silica from aqueous and non-aqueous media

A mesoporous silica (SBA-15) and amorphous silica (SG) have been chemically modified with 2-mercaptopyridine using the homogeneous route. This synthetic route involved the reaction of 2-mercaptopyridine with 3-chloropropyltriethoxysilane prior to immobilization on the support. The resulting material has been characterized by powder X-ray diffraction, nitrogen gas sorption, FT-IR and MAS NMR spectroscopy, thermogravimetry and elemental analysis. The solid was employed as a Cr(VI) adsorbent from aqueous and non-aqueous solutions at room temperature. The effect of several variables (stirring time, pH, metal concentration and solvent polarity) has been studied using the batch technique. The results indicate that under the optimum conditions, the maximum adsorption value for Cr(VI) was 1.83 ± 0.03 mmol/g for MP-SBA-15, whereas the adsorption capacity of the MP-SG was 0.86 ± 0.02 mmol/g. On the basis of these results, it can be concluded that it is possible to modify chemically SBA-15 and SG with 2-mercaptopyridine and to use the resulting modified silicas as effective adsorbents for Cr(VI).