Characterization of Cr(VI) removal from aqueous solutions by a surplus agricultural waste--rice straw

The removal of Cr(VI) from aqueous solution by rice straw, a surplus agricultural byproduct was investigated. The optimal pH was 2.0 and Cr(VI) removal rate increased with decreased Cr(VI) concentration and with increased temperature. Decrease in straw particle size led to an increase in Cr(VI) removal. Equilibrium was achieved in about 48 h under standard conditions, and Cr(III), which appeared in the solution and remained stable thereafter, indicating that both reduction and adsorption played a part in the Cr(VI) removal. The increase of the solution pH suggested that protons were needed for the Cr(VI) removal. A relatively high level of NO(3)(-) notably restrained the reduction of Cr(VI) to Cr(III), while high level of SO(4)(2-) supported it. The promotion of the tartaric acid modified rice straw (TARS) and the slight inhibition of the esterified rice straw (ERS) on Cr(VI) removal indicated that carboxyl groups present on the biomass played an important role in chromium remediation even though were not fully responsible for it. Isotherm tests showed that equilibrium sorption data were better represented by Langmuir model and the sorption capacity of rice straw was found to be 3.15 mg/g.     

Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water

Hexavalent chromium is a well-known highly toxic metal, considered a priority pollutant. Industrial sources of Cr(VI) include leather tanning, cooling tower blowdown, plating, electroplating, anodizing baths, rinse waters, etc. The most common method applied for chromate control is reduction of Cr(VI) to its trivalent form in acid (pH approximately 2.0) and subsequent hydroxide precipitation of Cr(III) by increasing the pH to approximately 9.0-10.0 using lime. Existing overviews of chromium removal only cover selected technologies that have traditionally been used in chromium removal. Far less attention has been paid to adsorption. Herein, we provide the first review article that provides readers an overview of the sorption capacities of commercial developed carbons and other low cost sorbents for chromium remediation. After an overview of chromium contamination is provided, more than 300 papers on chromium remediation using adsorption are discussed to provide recent information about the most widely used adsorbents applied for chromium remediation. Efforts to establish the adsorption mechanisms of Cr(III) and Cr(VI) on various adsorbents are reviewed. Chromium's impact environmental quality, sources of chromium pollution and toxicological/health effects is also briefly introduced. Interpretations of the surface interactions are offered. Particular attention is paid to comparing the sorption efficiency and capacities of commercially available activated carbons to other low cost alternatives, including an extensive table.     

Lifetime and regeneration of immobilized titania for photocatalytic removal of aqueous hexavalent chromium

Immobilized titania (TiO2) batch reactors reduced hexavalent chromium (Cr(VI)) in the form of potassium dichromate (K2Cr2O7) to trivalent chromium (Cr(III)) in aqueous solution at pH 3 under 171 W/m2 light intensity. The light source was a 125-W ultraviolet (UV) lamp. The Cr(VI) reduction showed zero-order kinetics (k0), while the Cr(VI) adsorption fitted with first-order kinetics (k(1st)). Adsorption capacity increased with increasing initial Cr(VI) concentration, and the area of immobilized TiO2 limited the reduction efficiency. The lifetime of fresh immobilized TiO2 was approximately 14 h. In addition, the regeneration of TiO2 with 3M sodium hydroxide (NaOH) was necessary to improve adsorption reaction.     

Removal of chromium from aqueous solution by using oxidized multiwalled carbon nanotubes

The batch removal of hexavalent chromium (Cr(VI)) from aqueous solution by using oxidized multiwalled carbon nanotubes (MWCNTs) was studied under ambient conditions. The effect of pH, initial concentration of Cr(VI), MWCNT content, contact time and ionic strength on the removal of Cr(VI) was also investigated. The removal was favored at low pH with maximum removal at pH <2. The adsorption kinetics was modeled by first-order reversible kinetics, pseudo-first-order kinetics, pseudo-second-order kinetics, and intraparticle diffusion models, respectively. The rate constants for all these kinetic models were calculated, and the results indicate that pseudo-second-order kinetics model was well suitable to model the kinetic adsorption of Cr(VI). The removal of chromium mainly depends on the occurrence of redox reaction of adsorbed Cr(VI) on the surface of oxidized MWCNTs to the formation of Cr(III), and subsequent the sorption of Cr(III) on MWCNTs appears as the leading mechanism for chromium uptake to MWCNTs. The presence of Cr(III) and Cr(VI) on oxidized MWCNTs was confirmed by the X-ray photoelectron spectroscopic analysis. The application of Langmuir and Freundlich isotherms are applied to fit the adsorption data of Cr(VI). Equilibrium data were well described by the typical Langmuir adsorption isotherm. Overall, the study demonstrated that MWCNTs can effectively remove Cr(VI) from aqueous solution under a wide range of experimental conditions, without significant Cr(III) release.     

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.     

Behavior of chromium and arsenic on activated carbon

The simultaneous adsorption of hexavalent chromium (Cr(VI)) and trivalent arsenic (As(III)) in single component and binary systems has been studied by activated carbon (AC). The capacity of Cr(VI) in the single experiment is greater than that of As(III) onto AC. The effects of various parameters like initial concentration, pH and temperature have been considered in the experiment. Cr(VI) removal is pH dependent and found to be maximum at pH 2.0. While, As(III) is found to be maximum at pH 7.0 in the single adsorption experiment. In the binary adsorption of As(III), the uptake of As(III) is generally higher than the single uptake. In the single adsorption the maximum adsorption rate of As(III) is 34% and in the binary metal mixtures the maximum adsorption rate of As(III) is 40% while the initial concentration is 5mg/L. So in the binary system the Cr(VI) and As(III) are thought to be synergistic with respect to the single As(III) situation.     

Coconut coir as biosorbent for Cr(VI) removal from laboratory wastewater

A high cost-effective treatment of sulphochromic waste is proposed employing a raw coconut coir as biosorbent for Cr(VI) removal. The ideal pH and sorption kinetic, sorption capacities, and sorption sites were the studied biosorbent parameters. After testing five different isotherm models with standard solutions, Redlich-Peterson and Toth best fitted the experimental data, obtaining a theoretical Cr(VI) sorption capacity (SC) of 6.3 mg g(-1). Acid-base potentiometric titration indicated around of 73% of sorption sites were from phenolic compounds, probably lignin. Differences between sorption sites in the coconut coir before and after Cr adsorption identified from Fourier transform infrared spectra suggested a modification of sorption sites after sulphochromic waste treatment, indicating that the sorption mechanism involves organic matter oxidation and chromium uptake. For sulphocromic waste treatment, the SC was improved to 26.8+/-0.2 mg g(-1), and no adsorbed Cr(VI) was reduced, remaining only Cr(III) in the final solution. The adsorbed material was calcinated to obtain Cr(2)O(3,) with a reduction of more than 60% of the original mass.     

Removal of chromium(III) from tannery wastewater using activated carbon from sugar industrial waste

Chromium is commonly found in huge quantities in tannery wastewaters. For this reason, the removal and recovery of the chromium content of tannery wastewaters is crucial for environmental protection and economic reasons. Removal and recovery of chromium were carried out by using low-cost potential adsorbents. For this purpose three types of activated carbon; C1, the waste generated from sugar industry as waste products and the others (C2, C3) are commercial granular activated carbon, were used. The adsorption process and extent of adsorption are dependent on the physical and chemical characteristics of the adsorbent, adsorbate and experimental condition. The effect of pH, particle size and different adsorbent on the adsorption isotherm of Cr(III) was studied in batch system. The sorption data fitted well with Langmuir adsorption model. The efficiencies of activated carbon for the removal of Cr(III) were found to be 98.86, 98.6 and 93 % for C1, C2 and C3, respectively. The order of selectivity is C1>C2>C3 for removal of Cr(III) from tannery wastewater. Carbon "C1" of the highest surface area (520.66 m(2)/g) and calcium content (333.3 mg/l) has the highest adsorptive capacity for removal of Cr(III). The results revealed that the trivalent chromium is significantly adsorbed on activated carbon collected from sugar industry as waste products and the method could be used economically as an efficient technique for removal of Cr(III) and purification of tannery wastewaters.     

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.     

The comprehensive investigation on removal mechanism of Cr(VI) by humic acid-Fe(II) system structured on V,Ti-bearing magnetite surface

The Cr(VI) could be adsorbed and reduced by the humic acid (HA)-Fe(II) system structured on the V, Ti-magnetite (VTM) surface. The Cr(VI) removal process included adsorption and reduction stages. First, the Cr(VI) was adsorbed on the VTM-HA surface via the ionic bonds between the Ti atoms of VTM core and the O atoms of the HCrO₄^?. The adsorption of Cr(VI) is uniform, monolayer, and controlled by Cr(VI) diffusion. Subsequently, the adsorbed Cr(VI) was reduced by the HA-Fe(II) system on the VTM-HA surface. During the Cr(VI) reduction process, the HA and Fe(II) have a synergistic effect. The Cr(VI) was reduced to the Cr(III) by the HA and Fe(II). Meanwhile, the HA could also reduce Fe(III) to Fe(II), making Fe(II) continue to participate in the Cr(VI) reduction. The olefin, hydroxyl, and aldehyde groups of HA were the primary electron donors during the Cr(VI) reduction. The Fe(II) acted as an electron bridge, transferring the electron from HA to Cr(VI). The reduced Cr(III) was deposited on the VTM-HA surface via the complexation with the carboxyl and hydroxyl groups of HA. The results demonstrated that the Cr(VI) could be adsorbed, reduced and complexed by the HA-Fe(II) system on the VTM-HA surface synchronously.     

Removal of chromium ions from [corrected] aqueous solutions by adsorption on activated carbon and char

Adsorption isotherms of chromium ions in aqueous solution have been experimentally measured on a granular activated carbon (GAC) and on a char of South African coal (CSAC). Experimental results show that the adsorption capacity for the GAC strongly depends on solution pH and salinity, with maximum values around 7mg/g at neutral pH and low salinity levels. On the contrary, the CSAC shows a smaller adsorption capacity, near 0.3mg/g, which slightly decreases by increasing pH and salinity levels. Chromium adsorption mainly depends on the availability of chromium ions in solution and on the occurrence of redox reactions between the surface groups and the Cr(VI) which lead to the formation of Cr(III). The reduction of Cr(VI) and the following sorption of Cr(III) cations appears as the leading mechanism for chromium uptake on the CSAC. A similar behaviour can be observed for the GAC at pH below 3. On the contrary, at pH>7, the multicomponent competitive adsorption of Cr(VI), OH(-) and Cl(-) has to be considered.     

Adsorption and mobility of Cr(III)-organic acid complexes in soils

The soluble Cr(III) is likely to be complexed with organic ligands in ligand-rich soil. Cr(VI) chemical reduction by organic acids and bioreduction by microorganisms can produce soluble Cr(III)-organic acids complexes. Thus, it is of great significance to investigate the absorption and mobility of Cr(III)-organic acid complexes in soils. In this study, Cr(III)-EDTA and Cr(III)-cit were prepared and purified, and then were examined for adsorption and mobility. The results demonstrated that Cr(III) was strongly bound to soil, while Cr(III)-organic acid complexes had no or slight interaction with soils since Cr(III)-EDTA and Cr(III)-cit complexes mainly existed as the forms of [Cr(III)-EDTA]⁻ and [Cr(III)-cit], respectively, under the tested conditions with initial pH 4.0-9.0. The adsorption of Cr(III) increased but that of Cr(III)-organic acid complexes decreased with the content of soil organic matter. Compared with Cr(III)-EDTA, the mobility of Cr(III)-cit in soil columns was reduced, due to the specific adsorption between soils and Cr(III)-cit which contained one free hydroxyl group.     

Trivalent chromium removal from wastewater using low cost activated carbon derived from agricultural waste material and activated carbon fabric cloth

An efficient adsorption process is developed for the decontamination of trivalent chromium from tannery effluents. A low cost activated carbon (ATFAC) was prepared from coconut shell fibers (an agricultural waste), characterized and utilized for Cr(III) removal from water/wastewater. A commercially available activated carbon fabric cloth (ACF) was also studied for comparative evaluation. All the equilibrium and kinetic studies were conducted at different temperatures, particle size, pHs, and adsorbent doses in batch mode. The Langmuir and Freundlich isotherm models were applied. The Langmuir model best fit the equilibrium isotherm data. The maximum adsorption capacities of ATFAC and ACF at 25 degrees C are 12.2 and 39.56 mg/g, respectively. Cr(III) adsorption increased with an increase in temperature (10 degrees C: ATFAC--10.97 mg/g, ACF--36.05 mg/g; 40 degrees C: ATFAC--16.10 mg/g, ACF--40.29 mg/g). The kinetic studies were conducted to delineate the effect of temperature, initial adsorbate concentration, particle size of the adsorbent, and solid to liquid ratio. The adsorption of Cr(III) follows the pseudo-second-order rate kinetics. From kinetic studies various rate and thermodynamic parameters such as effective diffusion coefficient, activation energy and entropy of activation were evaluated. The sorption capacity of activated carbon (ATFAC) and activated carbon fabric cloth is comparable to many other adsorbents/carbons/biosorbents utilized for the removal of trivalent chromium from water/wastewater.     

Adsorption of chromium(VI) on pomace--an olive oil industry waste: batch and column studies

The waste pomace of olive oil factory (WPOOF) was tested for its ability to remove chromium(VI) from aqueous solution by batch and column experiments. Various thermodynamic parameters, such as DeltaG degrees , DeltaH degrees and DeltaS degrees have been calculated. The thermodynamics of chromium(VI) ion onto WPOOF system indicates spontaneous and endothermic nature of the process. The ability of WPOOF to adsorb chromium(VI) in a fixed bed column was investigated, as well. The effect of operating parameters such as flow rate and inlet metal ion concentration on the sorption characteristics of WPOOF was investigated. The longest breakthrough time and maximum of Cr(VI) adsorption is obtained at pH 2.0. The total adsorbed quantities, equilibrium uptakes and total removal percents of chromium(VI) related to the effluent volumes were determined by evaluating the breakthrough curves obtained at different flow rates and different inlet chromium(VI) concentrations for adsorbent. The data confirmed that the total amount of sorbed chromium(VI) and equilibrium chromium(VI) uptake decreased with increasing flow rate and increased with increasing inlet chromium(VI) concentration. The Adams-Bohart model were used to analyze the experimental data and the model parameters were evaluated.     

Adsorption of Cr(VI) using silica-based adsorbent prepared by radiation-induced grafting

Silica-based adsorbent was prepared by radiation-induced grafting of dimethylaminoethyl methacrylate (DMAEMA) onto the silanized silica followed by a protonation process. The FTIR spectra and XPS analysis proved that DMAEMA was grafted successfully onto the silica surface. The resultant adsorbent manifested a high ion exchange capacity (IEC) of ca. 1.30 mmol/g and the Cr(VI) adsorption behavior of the adsorbent was further investigated, revealing the recovery of Cr(VI) increased with the adsorbent feed and the equilibrium adsorption could be achieved within 40 min. The adsorption capacity, strongly depended on the pH of the solution, reached a maximum Cr(VI) uptake (ca. 68 mg/g) as the pH was in the range of 2.5–5.0. Furthermore, even in strong acidic (4.0 mol/L HNO₃) or alkaline media (pH 11.0), the adsorbent had a sound Cr(VI) uptake capacity (ca. 22 and 30 mg/g, respectively), and the adsorption followed Langmuir mode. The results indicated that this adsorbent, prepared via a convenient approach, is applicable for removing heavy-metal-ion pollutants (e.g. Cr(VI)) from waste waters.     

Removal of chromium and toxic ions present in mine drainage by Ectodermis of Opuntia

This work presents conditions for hexavalent and trivalent chromium removal from aqueous solutions using natural, protonated and thermally treated Ectodermis of Opuntia. A removal of 77% of Cr(VI) and 99% of Cr(III) can be achieved. The sorbent material is characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, infrared spectroscopy, thermogravimetric analysis, before and after the contact with the chromium containing aqueous media. The results obtained from the characterization techniques indicate that the metal ion remains on the surface of the sorbent material. The percentage removal is found to depend on the initial chromium concentration and pH. The Cr(VI) and Cr(III) uptake process is maximum at pH 4, using 0.1g of sorbent per liter of aqueous solution. The natural Ectodermis of Opuntia showed a chromium adsorption capacity that was adequately described by the Langmuir adsorption isotherm. Finally, an actual mine drainage sample that contained Cd, Cr, Cu, Fe Zn, Ni and Pb was tested under optimal conditions for chromium removal and Ectodermis of Opuntia was found to be a suitable sorbent material. The use of this waste material for the treatment of metal-containing aqueous solutions as well as mine drainage is effective and economical.     

A comparative study of two chelating ion-exchange resins for the removal of chromium(III) from aqueous solution

Macroporous resins containing iminodiacetic acid (IDA) groups (Lewatit TP 207 and Chelex-100) were investigated as a function of concentration, temperature and pH for their sorption properties towards chromium(III). The chromium(III) ions sorbed onto the resin and in the equilibrium concentration were determined by inductively coupled plasma spectrophotometer. The maximum sorption for chromium ions was observed at pH 4.5. Solution pH had a strong effect on the equilibrium constant of Cr(III). The equilibrium constants were 320 and 7 at pH value 4.5 for Lewatit TP 207 and Chelex-100 resin, respectively. The Langmuir isotherm was used to describe observed sorption phenomena. Both the sorbents had high bonding constants with Lewatit TP 207 showing stronger binding. The equilibrium related to adsorption capacity and energy of adsorption was obtained by using plots of Langmuir adsorption isotherm. It was observed that the maximum adsorption capacity of 0.288 mmol of Cr(III)/g for Chelex-100 and 0.341 mmol of Cr(III)/g for Lewatit TP 207 was achieved at pH of 4.5. The rise in temperature caused a slight increase in the value of the equilibrium constant (K_c) for the sorption of chromium(III) ion.     

Adsorption characteristics and separation of Cr(III) and Cr(VI) on hydrous titanium(IV) oxide

A hydrous titanium(IV) oxide was prepared to study the adsorption characteristics and the separation of chromium species. Batch sorption studies have been carried out to determine the effect of pH on the sorption of Cr(III) and Cr(VI) on hydrous TiO2. An excellent separation efficiency of Cr(III) and Cr(VI) was obtained at pH 2. The adsorption percentage of Cr(VI) was above 99%, whereas that of the Cr(III) was less than 1% at this pH. The adsorption isotherm of Cr(VI) on hydrous TiO2 at pH 2 was in good agreement with the Langmuir isotherm. The maximum adsorption capacity of Cr(VI) on TiO2 was 5 mg g(-1). The rate of adsorption of Cr(VI) by hydrous TiO2 with average particle diameter 250 and 500 microm has been studied under particle diffusion controlled conditions. The diffusion coefficients of Cr(VI) for both hydrous TiO2 having average particle diameter of 250 and 500 microm was calculated at pH 2 as 3.84 x 10(-10) m2 s(-1) and 8.86 x 10(-10) m2 s(-1), respectively.     

Removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles

Diatomite-supported/unsupported magnetite nanoparticles were prepared by co-precipitation and hydrosol methods, and characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the unsupported and supported magnetite nanoparticles are around 25 and 15 nm, respectively. The supported magnetite nanoparticles exist on the surface or inside the pores of diatom shells, with better dispersing and less coaggregation than the unsupported ones. The uptake of hexavalent chromium [Cr(VI)] on the synthesized magnetite nanoparticles was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium [Cr(III)]. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed a pseudo-second-order model. The adsorption data of diatomite-supported/unsupported magnetite fit well with the Langmuir isotherm equation. The supported magnetite showed a better adsorption capacity per unit mass of magnetite than unsupported magnetite, and was more thermally stable than their unsupported counterparts. These results indicate that the diatomite-supported/unsupported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.     

A comparative study of the removal of trivalent chromium from aqueous solutions by bentonite and expanded perlite

Local bentonite and expanded perlite (Morocco) have been characterised and used for the removal of trivalent chromium from aqueous solutions. The kinetic study had showed that the uptake of Cr(III) by bentonite is very rapid compared to expanded perlite. To calculate the sorption capacities of the two sorbents, at different pH, the experimental data points have been fitted to the Freundlich and Langmuir models, respectively, for bentonite and expanded perlite. For both sorbents the sorption capacity increases with increasing the pH of the suspensions. The removal efficiency has been calculated for both sorbents resulting that bentonite (96% of Cr(III) was removed) is more effective in removing trivalent chromium from aqueous solution than expanded perlite (40% of Cr(III) was removed). In the absence of Cr(III) ions, both bentonite and expanded perlite samples yield negative zeta potential in the pH range of 2-11. The changes of expanded perlite charge, from negative to positive, observed after contact with trivalent chromium(III) solutions was related to Cr(III) sorption on the surface of the solid. Thus, it was concluded that surface complexation plays an important role in the sorption of Cr(III) species on expanded perlite. In the case of bentonite, cation-exchange is the predominate mechanism for sorption of trivalent chromium ions, wherefore no net changes of zeta potential was observed after Cr(III) sorption. X-ray photoelectron spectroscopy measurements, at different pH values, were also made to corroborate the zeta potential results.