Effects of anion species and concentration on the removal of Cr(VI) by a microalgal isolate, Chlorella miniata

The presence of nitrate, chloride and sulfate anions on the removal of Cr(VI) by Chlorella miniata was investigated. Results of kinetic studies indicated that the equilibrium time in each anion system increased with increases of the initial salt concentration, and the inhibitory order was NO(3)(-)>Cl(-)>SO(4)(2-) for Cr(VI) removal and was SO(4)(2-)>Cl(-) approximately NO(3)(-) for the biosorption of the bioreduced Cr(III). The inhibitory effect caused by different anions was attributed to biosorption mechanism and metal speciation. Since both biosorption and bioreduction were involved in Cr(VI) removal, the presence of anions could compete with Cr(VI) for the adsorption sites, and the affinity of anions to the algal biomass followed the order of NO(3)(-)>Cl(-)>SO(4)(2-), which was consistent with their inhibitory order on Cr(VI) removal. Speciation results also indicated that the formation of CrO(3)SO(4)(2-) in the sulfate system made it easier to be adsorbed on the biomass than HCrO(4)(-). The biosorption-bioreduction model further suggested that the bioreduction rate constant k decreased with increases of anion concentrations ranging from 0 to 0.5M, and followed the order of SO(4)(2-)>Cl(-)>NO(3)(-). The biosorption constant b also decreased with anion concentrations in the range of 0-0.2M, suggesting that this parameter was more sensitive to anion effects than the k values. The higher b values in the sulfate than in the nitrate and chloride systems indicated that Cr(VI) in the sulfate system was more easily adsorbed on the algal biomass. These findings demonstrated that the presence of anions significantly affected the removal of Cr(VI) by C. miniata. Since chloride, nitrate and sulfate ions are commonly found in industrial wastewater, it may be necessary to eliminate these ions prior to chromium removal.     

Biosorption of copper(II) by nonliving lichen biomass of Cladonia rangiformis hoffm

Biosorption of heavy metals can be an effective process for the removal of heavy metal ions from aqueous solutions. In this study, the adsorption properties of lichen biomass of Cladonia rangiformis hoffm. for copper(II) were investigated by using batch adsorption techniques. The effects of initial metal ion concentration, initial pH, biosorbent concentration, stirring speed and contact time on biosorption efficiency were studied. In the experiments the optimum pH value was found out 5.0 which was the native pH value of solution. The experimental adsorption data were fitted to the Langmuir adsorption model. The highest metal uptake was calculated from Langmuir isotherm and found to be 7.6923 mg Cu(II)/g inactivated lichen at 15 degrees C. The results indicated that the biomass of C. rangiformis is a suitable biosorbent for removing Cu(II) from aqueous solutions.     

Copper(II) and zinc(II) biosorption on Pinus sylvestris L

The biosorption properties of copper(II) and zinc(II) onto a cone biomass of Pinus sylvestris L. was investigated by using batch techniques. The biosorption studies carried out with single metal solutions. The removal of copper(II) and zinc(II) from aqueous solution increased with pH and sharply decreased when pH of the solution was decreased. The maximum biosorption efficiency of P. sylvestris was 67% and 30% for Cu(II) and Zn(II), respectively. Batch kinetic and isotherm of biosorption metal ions were investigated. The second-order kinetic model was used to correlate the experimental data. The Freundlich and Langmuir model can describe the adsorption equilibrium of metal(II) on cone biomass. The biosorption constants were found from the Freundlich and Langmuir isotherms at 25 degrees C. It is found that the biosorption data of metals on cone biomass fitted both the Freundlich and Langmuir adsorption models.     

Biosorption of heavy metal ions from aqueous solution by red macroalgae

Biosorption is an effective process for the removal and recovery of heavy metal ions from aqueous solutions. The biomass of marine algae has been reported to have high biosorption capacities for a number of heavy metal ions. In this study, four species of red seaweeds Corallina mediterranea, Galaxaura oblongata, Jania rubens and Pterocladia capillacea were examined to remove Co(II), Cd(II), Cr(III) and Pb(II) ions from aqueous solution. The experimental parameters that affect the biosorption process such as pH, contact time and biomass dosage were studied. The maximum biosorption capacity of metal ions was 105.2mg/g at biomass dosage 10 g/L, pH 5 and contact time 60 min. The biosorption efficiency of algal biomass for the removal of heavy metal ions from industrial wastewater was evaluated for two successive cycles. Galaxaura oblongata biomass was relatively more efficient to remove metal ions with mean biosorption efficiency of 84%. This study demonstrated that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for lowering the heavy metal pollution in the environment.     

Identification and characterization of Leucobacter sp. N-4 for Ni (II) biosorption by response surface methodology

In the present study, batch experiments were carried out to characterize and optimize the removal process of Ni (II) by a nickel tolerant strain Leucobacter sp. N-4, which was isolated from the soil samples. The effects of operating parameters with respect to initial solution pH (3.0-6.5), initial nickel concentration (50-100mg/L) and biomass dosage (1-10 g/L) on Ni (II) biosorption were investigated by response surface methodology (RSM). The maximal Ni (II) removal efficiency (nearly 99%) was achieved under the following conditions: pH 4.75, biomass dosage 5.38 g/L and initial Ni (II) concentration 53.6 mg/L. The adsorption-equilibrium data fitted well with both Langmuir and Freundlich isotherms. The monolayer adsorption capacity of biomass obtained from Langmuir isotherm was about 19.6 mg/g. Infrared spectrometer (IR) results showed that chemical functional groups (e.g. -NH(2), -OH and COO-M) of the biomass should be the active binding sites for Ni (II) biosorption from aqueous solutions.     

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.     

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 characteristics of anionic metals by micellar-enhanced ultrafiltration

Surfactant-based separation of Fe(CN)(6)(3-) and CrO(4)(2-) using regenerated cellulose membrane was studied in order to assess the potential of micellar-enhanced ultrafiltration for the remediation of wastewater or groundwater polluted with ferriccyanide and chromate. In the ferriccyanide/octadecylamine acetate (ODA) and chromate/ODA systems, removal of ferriccyanide increased from 73 to 92% and to 98%, and that of chromate from 64 to 97% and to >99.9% as the molar ratio of ODA to ferriccyanide and to chromate increased from 1 to 2 and to 3, respectively. In the ferriccyanide/chromate/ODA system, while the removal of ferriccyanide increased from 62 to 72% and to 93%, the removal of chromate from 20 to 38% and to 68% as the molar ratio of ferriccyanide:chromate:ODA increased from 1:1:1 to 1:1:2 and to 1:1:4, respectively. With the molar ratio of 1:1:6, the removal was >99.9 and 98% for chromate and ferriccyanide, respectively. Ferriccyanide ions were more easily bound to ODA micelles because the binding power of ferriccyanide was greater than that of chromate.     

Ni(II) removal from aqueous solutions using cone biomass of Thuja orientalis

The biomass of terrestrial-plant materials has high removal capacities for a number of heavy metal ions. The Ni(II) biosorption capacity of the cone biomass of Thuja orientalis was studied in the batch mode. The biosorption equilibrium level was determined as a function of contact time, pH, temperature, agitation speed at several initial metal ion and adsorbent concentrations. The removal of Ni(II) from aqueous solutions increased with adsorbent concentration, temperature and agitation speed of the solution were increased. The biosorption process was very fast; 90% of biosorption occurred within 3 min and equilibrium was reached at around 7 min. It is found that the biosorption of Ni(II) on the cone biomass was correlated well (R2 > 0.99) with the Langmuir equation as compared to Freundlich, BET Temkin and D-R isotherm equation under the concentration range studied. According to Langmuir isotherm, the monolayer saturation capacity (Q(o)) is 12.42 mg g(-1). The pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models were applied to test the experimental data for initial Ni(II) and cone biomass concentrations. The pseudo-second-order kinetic model provided the best correlation of the used experimental data compared to the pseudo-first-order and intraparticle diffusion kinetic models. The activation energy of biosorption (E(a)) was determined as 36.85 kJ mol(-1) using the Arrhenius equation. This study indicated that the cone biomass of T. orientalis can be used as an effective and environmentally friendly adsorbent for the treatment of Ni(II) containing aqueous solutions.     

Removal and recovery of nickel(II) from aqueous solution by loofa sponge-immobilized biomass of Chlorella sorokiniana: characterization studies

The biosorption process for the removal of nickel(II) by loofa sponge-immobilized biomass of Chlorella sorokiniana (LIBCS), a newly developed immobilized biosorbent, was characterized. Effects of environmental factors on metal uptake capacity of LIBCS were studied and compared with free biomass of C. sorokiniana (FBCS). Nickel(II) removal by LIBCS was found to be influenced by pH of the solution, initial metal concentration, and biomass concentration. The biosorption of nickel(II) ions by both LIBCS and FBCS increased as the initial concentration of nickel(II) ions increased in the medium. No loss to biosorption capacity of LIBCS for nickel(II) was found due to the presence of loofa sponge, indeed as compared to FBCS an increase of 25.3% was noted in the biosorption capacity of LIBCS. Maximum biosorption capacities for FBCS and LIBCS were found as 48.08 and 60.38 mg nickel(II)/g, respectively, whereas the amount of nickel(II) ions adsorbed on the plain loofa sponge was 6.1mg/g. During these biosorption studies, LIBCS exhibited excellent physical and chemical stability without any significant release/loss of microalgal biomass from loofa sponge matrix. The kinetics of nickel(II) removal was extremely fast reaching at equilibrium in about 15 min for LIBCS and 20 min for FBCS. The biosorption equilibrium was well described by the Langmuir and Freundlich adsorption isotherms. The biosorption capacities were found to be solution pH dependent and the maximum adsorption was found at a solution pH 4-5. The LIBCS could be regenerated using 75 mM HCl, with up to 98% recovery. The LIBCS were shown to be robust and stable with little decrease in the nickel(II) uptake capacity when used in consecutive seven biosorption-desorption cycles. Continuous removal of nickel(II) from electroplating effluent by LIBCS packed in fixed bed column bioreactor confirm the possibility of developing a biological treatment process for the removal of toxic metals from authentic wastewater.     

Factors influencing the removal of fluoride from aqueous solution by calcined Mg-Al-CO3 layered double hydroxides

Layered double hydroxides (LDH) calcined at different temperatures (denoted as CLDH) have been demonstrated to recover their original layered structure in the presence of appropriate anions. In the light of this so-called "memory effect", a study of removal of fluoride from aqueous solution by calcined Mg-Al-CO(3)-LDH has been carried out. The LDH calcined at 500 degrees C had the highest capacity of removal of fluoride ion, because of retention of its intrinsic structure. The CLDH with an Mg/Al ratio of 2 has a remarkable ability to adsorb anions. The adsorption loading is higher for the calcined Mg-Al-LDH than for calcined Zn-Al and Ni-Al-LDH. The influence of varying the conditions for removal of fluoride, such as the pH of aqueous solution, the initial fluoride concentration, the dosage of adsorbent, and temperature on removal of fluoride have been investigated. The influence of co-existing anions in fluoride aqueous solution indicates that the percentage of removal of fluoride increased in order PO(4)(3-) < Cl(-) approximately SO(4)(2-) < Br(-) < NO(3)(-). It was found that maximum removal of fluoride from aqueous solutions was obtained in 6h at pH 6.0 with an initial concentration of 50 mg/L, and that the retention of fluoride ions by the CLDH material was 98% or higher. The residual fluoride concentration was found to be 0.4 mg/L with an initial concentration of 20 mg/L, which meets the national standard for drinking water quality. The Freundlich isotherm and Langmuir isotherm were used to fit the data of equilibrium experiments. The results of X-ray diffraction, FT-IR and TG-MS demonstrate that the adsorption phenomenon is accompanied by rehydration with concomitant uptake of fluoride ions to rebuild the initial layered structure.     

Reduction of chromate from electroplating wastewater from pH 1 to 2 using fluidized zero valent iron process

Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO(4)(2-)) to trivalent chromium (Cr(3+)) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH)(3(s)) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr(6+), pH 2 and ZVI dosage of 3g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe(3+) was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe(2+) but very low Fe(3+) was present. It can be explained that ZVI reacted with chromate to produce Fe(2+) first and the presence of chromate would keep converting Fe(2+) to Fe(3+). Therefore, Fe(2+) is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction.     

Concentration and purification of chromate from electroplating wastewater by two-stage electrodialysis processes

A designed two-stage electrodialysis system is proposed to concentrate and purify chromate from a low pH electroplating wastewater using monovalent selective electrodialysis membranes. With low pH of the raw water (pH 2.2) in the first stage, chromate was presented as HCrO(4)(-) and monovalent ions (HCrO(4)(-), NH(2)SO(3)(-), Na(+) and Cl(-)) were able to pass through the membrane thus chromate was concentrated up to 191%. Higher current density, flowrate and more membrane area all increased the chromium recovery. When pH was adjusted to 8.5 before entering the second stage, the chromate species was presented as divalent CrO(4)(2-) and retained in the concentrated stream, and the rest monovalent ions (NH(2)SO(3)(-), Na(+) and Cl(-)) were separated by passing through the membrane. For example, 45% of the chlorides were separated in this study. The separation efficiencies in the second stage were also increased when the current density, flowrate and membrane area were increased. Electron Spectroscopy for Chemical Analysis was used to examine the surface chromate species for stage 1, and anion exchange membrane showed more chromate fouling comparing to cation exchange membrane due to more adsorption and concentration polarization effects for the anion exchange membrane.     

Biosorption of mercury from aqueous solutions by powdered leaves of castor tree (Ricinus communis L.)

A new biosorbent produced from castor leaves powder [Ricinus communis L.] was used to remove mercury(II) from aqueous solutions. The initial mercury concentrations, contact time and initial pH were evaluated. The ability of castor leaves to remove mercury at various pH (2-8) was studied. The maximum capacity (Qmax) of biomass was found to be 37.2mg Hg(II)/g at pH 5.5. Biosorption equilibrium was established in approximately 1h. The equilibrium data were described well by Langmuir and Freundlich models. The adsorbed mercury on biomass was desorbed using 10 ml of 4M HCl solution. The biomass could be reused for other biosorption assays. The ability of biomass to adsorb mercury(II) in a column was investigated. These studies consider the possibility of using leaves of castor tree as an inexpensive adsorbent for the removal of Hg(II) from contaminated chemical and mining industry wastewaters. It is also suggested that the dried biomass might be simply kept and used in a very low cost metal ion removal system.     

Biosorption of Cr(III) from aqueous solution using algal biomass spirogyra spp

In the present investigation, a fresh water green algae spirogyra spp. was used as an inexpensive and efficient biosorbent for Cr(III) removal from aqueous solution. The algal biomass was treated with 0.1M NaOH, 0.2M CaCl(2) and 5% HCHO. The biosorption efficiency was compared with untreated biomass. The effects of various physico-chemical parameters were studied, e.g. pH 3.0-6.0, initial metal ions concentration 20-150mgL(-1), algal dose 1.0-3.0gL(-1), and contact time 15-180min, respectively. Biosorption of Cr(III) is highly pH dependent. Maximum 81.02% adsorption of Cr(III) was observed with 0.2M CaCl(2) treated biomass at pH 5.0. Removal of Cr(III) was more than 70% in 45min of contact time with different treated and untreated algal biomass at concentration 30mgL(-1). Maximum metal uptake (Q(max)) was observed as 30.21mgg(-1) with 0.2M CaCl(2) treated algal biomass indicate good biosorbents than other treated and untreated biomass. The high values of correlation coefficient (r(2)<0.90) indicate equilibrium data of treated and untreated form of algal biomass well fitted in Freundlich than Langmuir isotherms model equations.     

Direct spectrophotometric analysis of Cr(VI) using a liquid waveguide capillary cell

Hexavalent chromium Cr(VI) is a notorious ground water contaminant toxic to humans and animals. Assessment of an exposure risk for aquatic receptors necessitates frequent Cr(VI) concentration data from a range of surface and groundwater locations at Cr(VI) contamination sites. In this work, we demonstrate that enhanced ultraviolet-visible (UV-vis) spectroscopy using a liquid waveguide capillary cell (LWCC) offers an easy-to-use and economical methodology for the determination of chromate anion CrO(4)(2-) in Hanford natural waters without chemical pretreatment and generation of hazardous waste. Direct determination of CrO(4)(2-) in actual surface and ground water samples with the complexities of competing ions, dissolved organics, and other potential interfering agents was achieved by measuring the chromate optical absorbance at 372 nm. For a 100 cm path length LWCC, the detection limit for chromate was found to be as low as 0.073 ppb. A quantitative relationship between the intensity of the absorbance signal and water pH allowed for the straightforward calculation of total Cr(VI) content in natural water. The described method is applicable for in-field monitoring of Cr(VI) in environmental water samples at trace levels.     

Removal of anionic metals by amino-organoclay for water treatment

We describe a facile and simple one-pot synthesis of water-soluble amino-organoclay under ambient conditions. The clay was used to successfully remove environmentally toxic anionic metals, such as arsenate, chromate, and ferricyanide. The electrostatic interactions between the anionic metals and the protonated amino (ammonium) groups of the amino-organoclay resulted in rapid precipitation, within 3 min, with a high removal capacity. The maximum removal capacities (in units of mg metal per g organoclay) of the amino-organoclay clay toward HAsO(4)(2-), CrO(4)(2-), or Fe(CN)(6)(3-) were, 30.73 mg/g, 34.67 mg/g, or 218.88 mg/g in case of 0.02 g, 0.03 g, and 0.005 g of the amino-organoclay, respectively. The removal efficiencies of 0.07 g, 0.09 g, and 0.03 g of the amino-organoclay whose dosage of clay was at the highest removal efficiency (%) for arsenate, chromate, and ferricyanide, respectively, presented 59.79%, 89.54%, and 97.43%. Furthermore, humic acid that ubiquitous in the organic matter present in water or soil environments, inhibited the removal rate of anionic metals, and thus the removal efficiencies toward all anionic metals were markedly reduced. Humic acid preferentially precipitated with the interaction of amino-organoclay prior to the anionic metals.     

Biosorption of Reactive Black 5 dye by Penicillium restrictum: the kinetic study

Biosorption of Reactive Black 5 (RB 5) dye onto dried Penicillium restrictum biomass was studied with respect to pH, contact time, biosorbent and dye concentrations. The effect of temperature on the biosorption efficiency was also carried out and the kinetic parameters were determined. Optimum initial pH, equilibrium time and biomass concentration for RB 5 dye were found to be 1.0, 75 min and 0.4 g dm(-3) at 20 degrees C, respectively. The maximum biosorption capacities (q(max)) of RB 5 dye onto dried P. restrictum biomass were 98.33 and 112.50mg (g biomass)(-1) at 175 mg dm(-3) initial dye concentration at 20 and 50 degrees C, respectively, and it was 142.04 mg (g biomass)(-1) at 200 mg dm(-3) initial dye concentration at 35 degrees C. The results indicate that the biosorption process obeys a pseudo-second-order kinetic model.     

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.