Adsorption of Cu(II) on Araucaria angustifolia wastes: determination of the optimal conditions by statistic design of experiments

Wastes of Araucaria angustifolia (named pinh?o) natural (PW) and also loaded with Congo red (CRP) were tested as low-cost adsorbents for Cu(II) removal from aqueous solutions. In order to reduce the total number of experiments to achieve the best conditions of the batch adsorption procedure, three sets of statistical designs of experiments were carried-out for each adsorbent. Initially, a full 2(4) factorial design for each adsorbent with two central points (18 experiments) were performed, to optimize the following factors: mass of adsorbent (m), pH, time of contact (t) and initial metallic ion concentration (Co). These results indicated that almost all the main factors and its interactions were significant. It was verified for both adsorbents, that a mass of 30.0mg leaded to higher Cu(II) uptake and that the best pH for Cu(II) adsorption was 5.6. In order to continue the batch adsorption optimization of the systems, a central composite surface analysis design with two factors (Co, t) containing 13 experiments, divided in to four cube points, four axial points and five centre points was carried-out for each adsorbent. By performing these two sets of statistical design of experiments, the best conditions for Cu(II) uptake using pinh?o wastes (PW) and pinh?o wastes loaded with Congo red (CRP) using batch adsorption system, where: m=30.0mg of adsorbent; pH 5.6; t=2.5h. After optimizing the batch adsorption system by statistical design of experiments, isotherms for Cu(II) uptake using PW and CRP were performed. These isotherms fitted to the linear Langmuir and Freundlich models.     

Biosorption of Cr(VI) by immobilized biomass of two indigenous strains of cyanobacteria isolated from metal contaminated soil

Biosorption of Cr(VI) using native strains of cyanobacteria from metal contaminated soil in the premises of textile mill has been reported in this paper. Biosorption was studied as a function of pH (1-5), contact time (5-180 min) and initial chromium ion concentration (5-20mg/l) to find out the maximum biosorption capacity of alginate immobilized Nostoc calcicola HH-12 and Chroococcus sp. HH-11. The optimum conditions for Cr(VI) biosorption are almost same for the two strains (pH 3-4, contact time 30 min and initial chromium concentration of 20mg/l) however, the biomass of Chroococcus sp. HH-11 was found to be more suitable for the development of an efficient biosorbent for the removal of Cr(VI) from wastewater, as it showed higher values of q(m) and K(f), the Langmuir and Freundlich isotherm parameters. Both the isotherm models were suitable for describing the biosorption of Cr(VI) by the cyanobacterial biosorbents.     

Application of a by-product of Lentinus edodes to the bioremediation of chromate contaminated water

The agricultural by-product of Lentinus edodes was used as a novel biosorbent for bioremediation of chromate contaminated waste water in the simulated experimental conditions. The contact time, particle size, biosorbent dosage and optimum pH range were investigated to optimize the sorption condition. The biosorption by the biomass was strongly affected by pH. At pH 1.0-2.5, all hexavalent chromium was diminished, either removed by the biosorbent or reduced to less toxic trivalent chromium even in very high concentration of 1000 mg/L. The adsorbed hexavalent chromium and reduced trivalent chromium were both linearly dependent on the initial chromium concentration. Most uptake of Cr occurred at pH around 4. The maximum uptake of chromium was 21.5 mg/g when simulated with Langmuir model, which showed the potential biosorption capacity of this biomaterial. The change of oxidation-reduction potential (ORP) during biosorption process revealed strong reduction ability of this biosorbent. Comparing analysis from Fourier transform infrared spectrums indicated that nitrogen oxide and carboxyl groups were increased after biosorption. The energy-dispersive X-ray microanalyzer revealed the mechanism of cation exchange during biosorption.     

Cr(VI) and Cr(III) speciation on Bacillus sphaericus loaded diaion SP-850 resin

A speciation procedure for chromium(III) and chromium(VI) in the environmental samples has been established in the presented work. The procedure presented based on quantitative biosorption of chromium(III) on Bacillus sphaericus loaded Diaion SP-850 at pH 5. The Cr(VI) recoveries at pH 5 were below 5% on the biosorbent. After reduction of Cr(VI) by concentrated H(2)SO(4) and ethanol, the system was applied to the total chromium. Cr(VI) was calculated as the difference between the total chromium content and the Cr(III) content. Optimal analytical conditions including pH, amounts of biosorbent, etc. for Cr(III) recoveries were investigated. The influences of the some alkaline and earth alkaline ions and some transition metals on the recoveries were also investigated. The capacity of biosorbent for chromium(III) was 6.95 mgg(-1). The detection limit (3 sigma) of the reagent blank for chromium(III) was 0.50 microgL(-1). The procedure was successfully applied to the speciation of chromium(III) and chromium(VI) in natural water samples (R.S.D. lower than 5%, recoveries greater than 95%).     

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.     

Biosorption of hexavalent chromium by raw and acid-treated green alga Oedogonium hatei from aqueous solutions

The hexavalent chromium, Cr(VI), biosorption by raw and acid-treated Oedogonium hatei were studied from aqueous solutions. Batch experiments were conducted to determine the biosorption properties of the biomass. The optimum conditions of biosorption were found to be: a biomass dose of 0.8 g/L, contact time of 110 min, pH and temperature 2.0 and 318 K respectively. Both Langmuir and Freundlich isotherm equations could fit the equilibrium data. Under the optimal conditions, the biosorption capacities of the raw and acid-treated algae were 31 and 35.2 mg Cr(VI) per g of dry adsorbent, respectively. Thermodynamic parameters showed that the adsorption of Cr(VI) onto algal biomass was feasible, spontaneous and endothermic under studied conditions. The pseudo-first-order kinetic model adequately describe the kinetic data in comparison to second-order model and the process involving rate-controlling step is much complex involving both boundary layer and intra-particle diffusion processes. The physical and chemical properties of the biosorbent were determined and the nature of biomass-metal ions interactions were evaluated by FTIR analysis, which showed the participation of -COOH, -OH and -NH(2) groups in the biosorption process. Biosorbents could be regenerated using 0.1 M NaOH solution, with up to 75% recovery. Thus, the biomass used in this work proved to be effective materials for the treatment of chromium bearing aqueous solutions.     

Application of response surface methodology for optimization of lead biosorption in an aqueous solution by Aspergillus niger

Response surface methodology was applied to optimize the removal of lead ion by Aspergillus niger in an aqueous solution. Experiments were conducted based on a rotatable central composite design (CCD) and analyzed using response surface methodology (RSM). The biosorption process was investigated as a function of three independent factors viz. initial solution pH (2.8-7.2), initial lead concentration (8-30 mg/l) and biomass dosage (1.6-6 g/l). The optimum conditions for the lead biosorption were found to be 3.44, 19.28 mg/l and 3.74 g/l, respectively, for initial solution pH, initial lead ion concentration and biomass dosage. Lead biosorption capacity on dead A. niger fungal biomass was enhanced by pretreatment using NaOH. Under these conditions, maximum biosorption capacity of the biomass for removal of lead ions was obtained to 96.21%. The desirability function was used to evaluate all the factors and response in the biosorption experiments in order to find an optimum point where the desired conditions could be obtained. The A. niger particles with clean surface and high porosity may have application as biosorbent for heavy metal removal from wastewater effluents.     

Removal of copper(II) and chromium(VI) from aqueous solution using sorghum roots (<Emphasis Type="Italic">S. bicolor</Emphasis>): a kinetic and thermodynamic study

Biosorption of toxic metal ions from industrial effluents using different plant parts is an important branch of environmental chemistry. Biosorption of copper(II) and chromium(VI) ions from aqueous solution onto sorghum root (SR) powder have been investigated under batch mode. The optimum pH and temperature for biosorption of both the metals was found to be 2 and 20 °C, respectively. The maximum biosorption capacity q _e for Cu(II) and Cr(VI) is 18.6 and 18.39 mg/g, respectively. The Langmuir model gave a better fit than other two models. The kinetic studies indicated that the biosorption process of the metal ions followed well pseudo-second-order model. The thermodynamic parameters were also calculated and the values indicated that the biosorption process was exothermic, spontaneous, and feasible in nature. Desorption experiments with 1 M HCl and 1 M HNO₃ inferred the reusability of biomass. The results showed that SRs have excellent adsorption properties and thus can be used as an effective and low cost biosorbent for the removal of Cu(II) and Cr(VI) ions from aqueous solution.     

Biosorption of chromium species by aquatic weeds: kinetics and mechanism studies

In this paper, we have presented the results of Cr(VI) and Cr(III) removal from aqueous phase by different aquatic weeds as biosorbents. Batch kinetic and equilibrium experiments were conducted to determine the adsorption kinetic rate constants and maximum adsorption capacities of selected biosorbents. In most of the cases, adsorption followed a second-order kinetics. For Cr(III), maximum adsorption capacity was exhibited by reed mat (7.18mg/g). In case of Cr(VI), mangrove leaves showed maximum removal/reduction capacity (8.87mg/g) followed by water lily (8.44mg/g). There was a significant difference in the concentrations of Cr(VI) and total chromium removed by the biosorbents. In case of Cr(VI) removal, first it was reduced to Cr(III) with the help of tannin, phenolic compounds and other functional groups on the biosorbent and subsequently adsorbed. Acid treatment significantly increased Cr(VI) removal capacity of the biosorbents whereas, alkali treatment reduced the Cr(VI) removal capacities of the biosorbents. FTIR spectrum showed the changes in functional groups during acid treatment and biosorption of Cr(VI) and Cr(III). Aquatic weeds seem to be a promising biosorbent for the removal of chromium ions from water environment.     

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 Cr(VI) and Ni(II) from aqueous solution by fused yeast: study of cations release and biosorption mechanism

Biosorption of Cr(VI) and Ni(II) by a fused yeast from Candida tropicalis and Candida lipolytica under varying range of pH, initial metal concentration and reaction time was investigated. Net cation release and Cr removal reached 2.000mmol/l and 81.37% when treating 20mg/l Cr(VI) at pH 2 with 25mg/l biomass for 30min, while for Ni were 0.351mmol/l and 64.60%, respectively. Trace metal elements such as Co, Cu, Mn, Mo, Se and Zn played active role in biosorption as important ingredients of functional enzymes. Cr(VI) was reduced to less toxic Cr(III) and chelated with extracellular secretions, and further accumulated inside the cells. For Ni biosorption, however, largely a passive uptake process influenced by ion gradient led to lower adsorption capacity and cations release. Fourier transform infrared (FTIR) spectrum analysis indicated that amide and pyridine on cells were involved in binding with Cr, but for Ni, bound-OH and nitro-compounds were the main related functional groups. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis confirmed that considerable amounts of metals precipitated on cell surface when dealing with high concentration metals.     

Box–Behnken Design optimization of malachite green dye biosortpion using nano zero valent iron Sargassum swartzii biocomposite

This study reports the biosorption of MG using a novel nano zero valent iron Sargassum swartzii (nZVI-SS) biocomposite. Response surface methodology derived from Box–Behnken design (BBD) was applied for optimizing the essential variables such as pH, initial MG concentration, and biosorbent dosage. The results obtained from BBD design showed the maximum biosorption capacity of 73.5?mg/g at pH 10, initial MG concentration of 100?mg/L, and biosorbent dosage of 0.55?g/L. The biosorption was highly dependent on pH and initial dye concentration. The nZVI-SS biocomposite was characterized using SEM, FTIR, TGA, and DSC analysis. The experimental and analytical result shows that nZVI-SS biocomposite can be effectively used as prominent biosorbent for the removal of dye bearing wastewater.     

Removal of Ni(II), Zn(II) and Cr(VI) from aqueous solution by Alternanthera philoxeroides biomass

Alternanthera philoxeroides biomass, a type of freshwater macrophyte, was used for the sorptive removal of Ni(II), Zn(II) and Cr(VI) from aqueous solutions. Variables of the batch experiments include solution pH, contact time, particle size and temperature. The biosorption capacities are significantly affected by solution pH. Higher pH favors higher Ni(II), Zn(II) removal, whereas higher uptake of Cr(VI) is observed as the pH is decreased. A two-stage kinetic behavior is observed in the biosorption of Ni(II), Zn(II) and Cr(VI): very rapid initial biosorption in a few minutes, followed by a long period of a slower uptake. It is noted that an increase in temperature results in a higher Ni(II), Zn(II) and Cr(VI) loading per unit weight of the sorbent. Decreasing the particle sizes of the Alternanthera philoxeroides biomass leads to an increase in the Ni(II), Zn(II) and Cr(VI) uptake per unit weight of the sorbent. All isothermal data are fairly well fitted with Langmuir equations. The thermodynamic parameter, DeltaG degrees, were calculated. The negative DeltaG degrees values of Cr(VI), Ni(II) and Zn(II) at various temperatures confirm the adsorption processes are spontaneous.     

Biosorption of Cr(VI) by native isolate of Lyngbya putealis (HH-15) in the presence of salts

Industrial wastewaters containing heavy metals along with high concentration of soluble salts pose a major environmental problem that needs to be remedied. The present study reports on biosorption of Cr(VI) by native isolate of Lyngbya putealis HH-15 in batch system under varying range of pH (2.0-10.0), initial metal ion concentration (10-100mg/l) and salt concentration (0-0.2%). Maximum metal removal (94.8%) took place at pH 3.0 with initial Cr concentration of 50mg/l, which got reduced (90.1%) in the presence of 0.2% salts. Adsorption equilibrium and kinetic behavior of Cr(VI) in solution was also examined. Both Langmuir and Freundlich models fitted well to explain the adsorption data (R(2)=0.90 and 0.87, respectively) at 0.2% salt concentration. Pseudo-second order kinetic model also fitted well to both the systems, viz. Cr(VI) and Cr(VI)+salt.     

Utilization of fermentation waste (Corynebacterium glutamicum) for biosorption of Reactive Black 5 from aqueous solution

A fermentation waste, Corynebacterium glutamicum, was successfully employed as a biosorbent for Reactive Black 5 (RB5) from aqueous solution. This paper initially studied the effect of pretreatment on the biosorption capacity of C. glutamicum toward RB5, using several chemical agents, such as HCl, H(2)SO(4), HNO(3), NaOH, Na(2)CO(3), CaCl(2) and NaCl. Among these reagents, 0.1M HNO(3) gave the maximum enhancement of the RB5 uptake, exhibiting 195mg/g at pH 1 with an initial RB5 concentration of 500mg/l. The solution pH and temperature were found to affect the biosorption capacity, and the biosorption isotherms derived at different pHs and temperatures revealed that a low pH (pH 1) and high temperature (35 degrees C) favored biosorption. The biosorption isotherm was well represented using three-parameter models (Redlich-Peterson and Sips) compared to two-parameter models (Langmuir and Freundlich models). As a result, high correlation coefficients and low average percentage error values were observed for three-parameter models. A maximum RB5 uptake of 419mg/g was obtained at pH 1 and a temperature of 35 degrees C, according to the Langmuir model. The kinetics of the biosorption process with different initial concentrations (500-2000mg/l) was also monitored, and the data were analyzed using pseudo-first and pseudo-second order models, with the latter describing the data well. Various thermodynamic parameters, such as DeltaG degrees, DeltaH degrees and DeltaS degrees, were calculated, indicating that the present system was a spontaneous and endothermic process. The use of a 0.1M NaOH solution successfully desorbed almost all the dye molecules from dye-loaded C. glutamicum biomass at different solid-to-liquid ratios examined.     

Biosorption of chromate anions from aqueous solution by a cationic surfactant-modified lichen (Cladonia rangiformis (L.))

Biosorption has been appearing as a useful alternative to conventional treatment systems for the removal of toxic metals from aqueous stream. The batch removal of chromate anions (CrO(4)(2-)) from wastewater under different experimental conditions using a cationic surfactant-modified lichen (Cladonia rangiformis (L.)) was investigated in this study. Cetyl trimethyl ammonium bromide (CTAB) was used for biomass modification. The results of the experiments showed that biomass modification substantially improved the biosorption efficiency. Effects of pH, biosorption time, initial CrO(4)(2-) concentration, biosorbent dosage, and the existence of the surfactant on the biosorption of CrO(4)(2-) anions were studied. Studies up to date have shown that the biosorption efficiency of chromium increased as the pH of the solution decreased. In the present study, the removal of chromate anions from aqueous solutions at high pH values with surfactant-modified lichen was investigated. From the results of the experiments it was seen that the removal of chromate anions by modified lichen was 61% at the solution natural pH (pH 5.11) but at the same pH value the removal of chromate anions by unmodified lichen was 6%. Also concentrations ranging from 30 to 150 mg/L Cr(IV) were tested and the biosorptive removal efficiency of the metal ions from aqueous solution at high pH was achieved more than 98%.     

Biosorption of chromium(VI) using Bacillus subtilis SS-1 isolated from soil samples of electroplating industry

Soils around the electroplating industry are often polluted with metals. The aim of the study was to assess Cr(VI) adsorption potential of chromium-resistant bacteria isolated from soil samples collected in and around electroplating industry, Coimbatore, India. A total of six morphologically different chromium-resistant bacteria were isolated from the soil samples and assayed for resistance to Cr(VI). Isolate designated SS-1 exhibited maximum resistance to Cr(VI) (600 mg/l) and subsequently identified as Bacillus subtilis based on the morphology, phenotypic characters, and partial 16S rDNA sequences. Batch experiments were carried out as a function of time, initial Cr(VI) concentration (100 mg/l), pH (2), and biosorbent dose (0.1 g/l). The maximum percentage of Cr(VI) removal was found to be 98.7 %. The experimental data showed a better fit with Langmuir model over Freundlich model throughout the range of initial concentrations. The kinetic models were examined with pseudo-first-order and pseudo-second-order kinetics. Fourier transform infrared spectroscopy studies confirmed the involvement of carboxyl and amide groups in Cr(VI) adsorption. Scanning electron microscopic studies revealed that nature of the bioadsorbent was altered after Cr(VI) adsorption. The results revealed that Cr(VI) was considerably adsorbed onto bacterial biomass, and it could be an economical method for the removal of Cr(VI) from aqueous solution.     

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.     

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 nickel from protonated rice bran

In the present study biosorption technique, the accumulation of metals by biomass was used for the removal of nickel from aqueous medium. The rice bran in its acid treated (H(3)PO(4)) form was used as a low cost sorbent. The adsorption characteristics of nickel on protonated rice bran were evaluated as a function of pH, biosorbent size, biosorbent dosage, initial concentration of nickel and time. Within the tested pH range (pH 1-7), the protonated rice bran displayed more resistance to pH variation, retaining up to 102 mg/g of the nickel binding capacity at pH 6. Meanwhile, at lower pH values the uptake capacity decreased. The % age removal of nickel was maximum at 0.25 g of biosorbent dose and 0.25 mm biosorbent size. At the optimal conditions, metal ion uptake was increased as the initial metal ion concentration increased up to 100mg/L. Kinetic and isotherm experiments were carried out at the optimal pH 6.0 for nickel. The metal removal rate was rapid, with 57% of the total adsorption taking place within 15-30 min. The Freundlich and Langmuir models were used to describe the uptake of nickel on protonated rice bran. The Langmuir and Freundlich model parameters were evaluated. The equilibrium adsorption data was better fitted to Langmuir adsorption isotherm model. The adsorption followed pseudo second-order kinetic model. The thermodynamic assessment of the metal ion-rice bran biomass system indicated the feasibility and spontaneous nature of the process and DeltaG degrees values were evaluated as ranging from -22.82 to -24.04 kJ/mol for nickel sorption. The order of magnitude of the DeltaG degrees values indicated an ion-exchange physiochemical sorption process.