Kinetic and thermodynamic studies of the biosorption of Cr(VI) by Pinus sylvestris Linn

Biosorption equilibrium, kinetics and thermodynamics of chromium(VI) ions onto cone biomass were studied in a batch system with respect to temperature and initial metal ion concentration. The biosorption efficiency of chromium ions to the cone biomass decreased as the initial concentration of metal ions was increased. But cone biomass of Pinus sylvestris Linn. exhibited the highest Cr(VI) uptake capacity at 45 degrees C. The biosorption efficiency increased from 67% to 84% with an increase in temperature from 25 to 45 degrees C at an initial Cr(VI) concentration of 300 mg/L. The Langmuir isotherm model was applied to experimental equilibrium data of Cr(VI) biosorption depending on temperature. According to Langmuir isotherm, the monolayer saturation capacity (Q(max)) is 238.10 mg/g. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data for initial Cr(VI). The pseudo-second-order kinetic model provided the best correlation of the used experimental data compared to the pseudo-first-order kinetic model. The activation energy of biosorption (E(a)) was determined as 41.74 kJ/mol using the Arrhenius equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of biosorption (DeltaG(0), DeltaH(0) and DeltaS(0)) were also evaluated.     

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.     

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.     

Modification of surface properties of Lentinus sajor-caju mycelia by physical and chemical methods: evaluation of their Cr6+ removal efficiencies from aqueous medium

The hexavalent chromium biosorption onto untreated and heat-, acid- and alkali-treated Lentinus sajor-caju mycelia were studied from aqueous solutions. The particles sizes of the fungal mycelia ranged from 100 to 200 microm. The effect of pH, temperature, biosorbent dose, initial concentration of chromium ions, contact time parameters were investigated in a batch system. Biosorption equilibrium was established in about 4 h. The surface charge density of the fungal preparations varied with pH, and the maximum absorption of chromium ions on the fungal preparations were obtained at pH 2.0. The biosorption of chromium ions by the tested fungal preparations increased as the initial concentration of chromium ions increased in the medium. The maximum biosorption capacities of the untreated and heat, HCl- and NaOH-treated fungal biomass were 0.363, 0.613, 0.478 and 0.513 mmol Cr6+ per gram of dry biomass, respectively. The correlation regression coefficients and the Langmuir constant values show that the biosorption process can be well defined by Langmuir equation. The chromium adsorption data were analysed using the first- and the second-order kinetic models. The first-order equation is the most appropriate equation to predict the biosorption capacities of all the fungal preparations. In addition, the polarity and surface energy of the untreated and all the modified biomass film preparations were determined by contact angle measurement. All the tested fungal biomass preparations could be regenerated using 0.1 M NaOH solution.     

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.     

Removal of Cr(VI) from aqueous solutions using pre-consumer processing agricultural waste: a case study of rice husk

This paper reports the feasibility of using pre-consumer processing agricultural waste to remove Cr(VI) from synthetic wastewater under different experimental conditions. For this, rice husk, has been used after pre-treatments (boiling and formaldehyde treatment). Effect of various process parameters, namely, pH, adsorbent dose, initial chromium concentration and contact time has been studied in batch systems. The removal of chromium was dependent on the physico-chemical characteristics of the adsorbent, adsorbate concentration and other studied process parameters. Maximum metal removal was observed at pH 2.0. The efficiencies of boiled and formaldehyde treated rice husk for Cr(VI) removal were 71.0% and 76.5% respectively for dilute solutions at 20gl(-1) adsorbent dose. The experimental data were analyzed using Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherm models. It was found that Freundlich and D-R models fitted well. The results revealed that the hexavalent chromium is considerably adsorbed on rice husk and it could be an economical method for the removal of hexavalent chromium from aqueous systems. FTIR and SEM were recorded, before and after adsorption, to explore number and position of the functional groups available for Cr(VI) binding on to studied adsorbents and changes in adsorbent surface morphology.     

Sorption and desorption studies of chromium(VI) from nonviable cyanobacterium Nostoc muscorum biomass

This communication presents results pertaining to the sorptive and desorptive studies carried out on chromium(VI) removal onto nonviable freshwater cyanobacterium (Nostoc muscorum) biomass. Influence of varying the conditions for removal of chromium(VI), such as the pH of aqueous solution, the dosage of biosorbent, the contact time with the biosorbent, the temperature for the removal of chromium, the effect of light metal ions and the adsorption-desorption studies were investigated. Sorption interaction of chromium on to cyanobacterial species obeyed both the first and the second-order rate equation and the experimental data showed good fit with both the Langmuir and freundlich adsorption isotherm models. The maximum adsorption capacity was 22.92 mg/g at 25 degrees C and pH 3.0. The adsorption process was endothermic and the values of thermodynamic parameters of the process were calculated. Various properties of the cyanobacterium, as adsorbent, explored in the characterization part were chemical composition of the adsorbent, surface area calculation by BET method and surface functionality by FTIR. Sorption-desorption of chromium into inorganic solutions and distilled water were observed and this indicated the biosorbent could be regenerated using 0.1 M HNO3 and EDTA with upto 80% recovery. The biosorbents were reused in five biosorption-desorption cycles without a significant loss in biosorption capacity. Thus, this study demonstrated that the cyanobacterial biomass N. muscorum could be used as an efficient biosorbent for the treatment of chromium(VI) bearing wastewater.     

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.     

Chromium(VI) removal from aqueous system using Helianthus annuus (sunflower) stem waste

The objective of this study was to investigate the Cr(VI) removal efficiency of sunflower waste from aqueous system under different process conditions. Two adsorbents were prepared by pre-treating the sunflower stem waste. One adsorbent was prepared by boiling it and second adsorbent was prepared by treating it with formaldehyde. Batch mode experiments were carried out as a function of solution pH, adsorbent dosage, Cr(VI) concentration and contact time. FT-IR spectra and SEMs of the adsorbents were recorded to explore the number and position of functional groups available for the binding of Cr(VI) ions and morphology of the studied adsorbents. The removal of chromium was dependent on the physico-chemical characteristics of the adsorbent, adsorbate concentration and other studied process parameters. Maximum metal removal was observed at pH 2.0. The efficiencies of boiled sunflower stem absorbent and formaldehyde-treated sunflower stem absorbent for the removal of Cr(VI) were 81.7 and 76.5%, respectively for dilute solutions at 4.0g/L adsorbent dose. The applicability of Langmuir, Freundlich and Dubinin-Radushkevich isotherms was also tested. The results revealed that the hexavalent chromium is considerably adsorbed on sunflower stem and it could be an economical method for the removal of hexavalent chromium from aqueous systems.     

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.     

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.     

Reduction of hexavalent chromium by Sphaerotilus natans a filamentous micro-organism present in activated sludges

Wastewaters produced by various industries may contain undesirable amounts of hexavalent chromium (Cr(VI)), as chromate and dichromate, a hazardous metal affecting flora and animals of aquatic ecosystems as well as human health. One removal strategy comprises the microbial reduction of Cr(VI) to Cr(III), a less soluble chemical species that is less toxic than Cr(VI). In this work, the ability to reduce Cr(VI) of Sphaerotilus natans, a filamentous bacterium usually found in activated sludge systems, was evaluated. In aerobic conditions, S. natans was able to efficiently reduce Cr(VI) to Cr(III) from dichromate solutions ranging between 4.5 and 80 mg Cr(VI)l(-1) in the presence of a carbonaceous source. A simultaneous evaluation of the microbial respiratory activity inhibition was also carried out to analyze the toxic effect of Cr(VI). Cr(VI) reduction by S. natans was mathematically modeled; chromium(VI) reduction rate depended on both Cr(VI) concentration and active biomass concentration. Although it is known that S. natans removes heavy metal cations such as Cr(III) by biosorption, the ability of this micro-organism to reduce Cr(VI), which behaves as an oxyanion in aqueous solutions, is a novel finding. The distinctive capacity to reduce Cr(VI) to Cr(III) than remain soluble or precipitated becomes S. natans a potential micro-organism to decontaminate wastewaters.     

Chromium (VI) adsorption on boehmite

Boehmite was synthesized and characterized in order to study the adsorption behavior and the removal of Cr(VI) ions from aqueous solutions as a function of contact time, initial pH solution, amount of adsorbent and initial metal ion concentration, using batch technique. Adsorption data of Cr(VI) on the boehmite were analyzed according to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption models. Thermodynamic parameters for the adsorption system were determinated at 293, 303, 313 and 323K temperatures. The kinetic values and thermodynamic parameters from the adsorption process show that the Cr(VI) ions adsorption on boehmite is an endothermic and spontaneous process. These results show that the boehmite could be considered as a potential adsorbent for chromium ions in aqueous solutions.     

Removal of chromium (VI) ions from aqueous solution by adsorption onto two marine isolates of Yarrowia lipolytica

The removal of chromium (VI) ions from aqueous solutions by the biomass of two marine strains of Yarrowia lipolytica (NCIM 3589 and 3590) was studied with respect to pH, temperature, biomass, sea salt concentration, agitation speed, contact time and initial concentration of chromium (VI) ions. Maximum biosorption was observed at pH 1.0 and at a temperature of 35 °C. Increase in biomass and sea salts resulted in a decreased metal uptake. With an agitation speed of 130 rpm, equilibrium was attained within 2 h. Under optimum conditions, biosorption was enhanced with increasing concentrations of Cr (VI) ions. NCIM 3589 and 3590 displayed a specific uptake of Cr (VI) ions of 63.73 ± 1.3 mg g⁻¹ at a concentration of 950 ppm and 46.09 ± 0.23 mg g⁻¹ at 955 ppm, respectively. Scatchard plot analysis revealed a straight line allowing the data to be fitted in the Langmuir model. The adsorption data obtained also fitted well to the Freundlich isotherm. The surface sequestration of Cr (VI) by Y. lipolytica was investigated with a scanning electron microscope equipped with an energy dispersive spectrometer (SEM-EDS) as well as with ED-X-ray fluorescence (ED-XRF). Fourier transform infrared (FTIR) spectroscopy revealed the involvement of carboxyl, hydroxyl and amide groups on the cell surfaces in chromium binding.     

Chromium(VI) biosorption by dried Rhizopus arrhizus: effect of salt (NaCl) concentration on equilibrium and kinetic parameters

Some industrial wastewaters contain high quantities of salts besides heavy metal ions. The presence of salt ions leads to high ionic strength, which may significantly affect the performance of the biosorption process so the effect of salts on the biosorption of heavy metal ions should be investigated. In this study the biosorption of chromium(VI) from saline solutions on dried Rhizopus arrhizus was studied as a function of pH, initial chromium(VI) and salt (NaCl) concentrations in a batch system. The biosorption capacity of R. arrhizus strongly depended on solution pH and maximum chromium(VI) sorption capacity of sorbent was obtained at pH 2.0 both in the absence and in the presence of increasing concentrations of salt. Chromium(VI)-salt biosorption studies were performed at this pH value. Equilibrium uptakes of chromium(VI) increased with increasing chromium(VI) concentration up to 250mgl(-1) and decreased considerably by the presence of increasing concentrations of salt. At 100mgl(-1), initial chromium(VI) concentration, dried R. arrhizus biosorbed 78.0mgg(-1) of chromium(VI) in 72h without salt medium. When salt concentration was raised to 50gl(-1), this value dropped to 64.0mgg(-1) of chromium(VI) at the same conditions resulting in 17.9% decrease of biosorption capacity. The equilibrium sorption data were analysed by using Freundlich, Langmuir, Redlich-Peterson and Langmuir-Freundlich (Sips), the two and three parameters adsorption models, using non-linear regression technique and isotherm constants were evaluated depending on salt concentration. The Langmuir-Freundlich (Sips) was the best suitable adsorption model for describing the biosorption of chromium(VI) individually and in salt-containing medium. Pseudo-first-order, pseudo-second-order and saturation type kinetic models described the biosorption kinetics accurately at all chromium(VI) concentrations in the absence and in the presence of changing concentrations of salt. Isotherm and saturation type kinetic constants varied due to the level of salt were expressed as a function of initial salt concentration.     

Single and binary chromium(VI) and Remazol Black B biosorption properties of Phormidium sp.

Wastewaters of textile and leather dying industries may contain significant quantities of chromium(VI) ions besides anionic and water-soluble dyes. Moreover the temperature of these wastewaters may be a controlling parameter affecting the biosorption efficiency. In this study biosorption of chromium(VI) and Remazol Black B reactive dye by dried Phormidium sp., a thermophilic cyanobacterium, was studied as a function of initial chromium(VI) concentration and temperature in no dye and 100 mg l⁻¹ dye-containing media at an initial pH value of 2.0 at which the biomass exhibited the maximum chromium(VI) and dye uptakes. The decrease of both metal and dye uptakes with temperature indicated that the uptakes were exothermic in nature. Equilibrium uptake of chromium(VI) enhanced considerably with both chromium(VI) and 100 mg l⁻¹ dye concentrations. Moreover the presence of chromium(VI) also increased the uptake of dye. At 25 °C, 22.8 mg g⁻¹ chromium(VI) and 91.3 mg g⁻¹ dye were sorbed by the biomass in binary 100 mg l⁻¹ chromium(VI) and 100 mg l⁻¹ dye-containing medium. The Langmuir was the best suitable adsorption model for describing the biosorption of chromium(VI) individually and in dye-containing medium. The pseudo-second-order kinetic model described both the chromium(VI) and dye biosorptions kinetics accurately.     

Pb(II) biosorption from hazardous aqueous streams using Gossypium hirsutum (Cotton) waste biomass

Studies on the biosorptive ability of Gossypium hirsutum (Cotton) waste biomass outlined that smaller size of biosorbent (0.355mm), higher biomass dose (0.20g), 5 pH and 100mg/L initial Pb(II) concentration were more suitable for enhanced Pb(II) biosorption from aqueous medium. The Langmuir isotherm model and pseudo second order kinetic model fitted well to the data of Pb(II) biosorption. Highly negative magnitude of Gibbs free energy (DeltaG degrees ) indicated that the process was spontaneous in nature. In addition to this surface coverage and distribution coefficient values of Pb(II) biosorption process were also determined. At optimized conditions Pb(II) uptake was more rapid in case of industrial effluents in comparison to synthetic solutions. FTIR spectroscopic analysis revealed that the main functional groups involved in the uptake of Pb(II) on the surface of G. hirsutum biomass were carboxyl, carbonyl, amino and alcoholic.     

Biosorption of zinc from aqueous solution using Azadirachta indica bark: equilibrium and kinetic studies

The removal of zinc ions from aqueous solutions on the biomass of Azadirachta indica bark has been studied by using batch adsorption technique. The biosorption studies were determined as a function of contact time, pH, initial metal ion concentration, average biosorbent size and biosorbent dosage. The equilibrium metal uptake was increased and percentage biosorption was decreased with an increase in the initial concentration and particle size of biosorbent. The maximum zinc biosorption occurred at pH 6 and percentage biosorption increases with increase in the biosorbent dosage. Experimental data obtained were tested with the adsorption models like Langmuir, Freundlich and Redlich-Peterson isotherms. Biosorption isothermal data were well interpreted by Langmuir model with maximum biosorption capacity of 33.49mg/g of zinc ions on A. indica bark biomass and kinetic data were properly fitted with the pseudo-second-order kinetic model.     

The use of sulphuric acid-carbonization products of sugar beet pulp in Cr(VI) removal

A carbon rich adsorbent prepared from the reaction of sugar beet pulp with sulphuric acid and gas formed during carbonization process have been studied for Cr(VI) removal from aqueous solutions. The SO(2) rich gas was shown to be an excellent Cr(VI) reductant. The equilibrium and kinetic studies were conducted by using the carbonaceous adsorbent derived from sugar beet pulp. The lower pH favoured Cr(VI) adsorption but substantial Cr(VI) reduction was observed. The Langmuir and Freundlich isotherm models were applied and the Langmuir model best fit the equilibrium isotherm data. The maximum adsorption capacity of chromium calculated from Langmuir isotherm is about 24 mgg(-1) for 25 degrees C. The adsorption of Cr(VI) is an endothermic process and follows the pseudo-second-order rate kinetics. The sulphuric acid-carbonization is an economical method for particularly chromium removal because the gas generated during carbonization exhibits good Cr(VI) reduction properties and carbonaceous material obtained is an efficient Cr(VI) adsorbent.     

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.