Biosorption of ammoniacal nitrogen from aqueous solutions with low-cost biomaterials: kinetics and optimization of contact time

The biosorption of ammoniacal nitrogen (N-NH₄ ⁺) from aqueous solutions by dead biomass of brown seaweed Cystoseira indica and Jatropha oil cake (JOC), which is generated in the process of biodiesel recovery from its seeds, was studied under diverse experimental conditions. The N-NH₄ ⁺ biosorption was strictly pH dependent, and maximum uptake capacity of C. indica (15.21 mg/g) and JOC (13.59 mg/g) was observed at initial pH 7 and 3, respectively. For each biosorbent–N-NH₄ ⁺ system, kinetic models were applied to the experimental data to examine the mechanisms of sorption and potential rate-controlling steps. The generalized rate model and pseudo-second-order kinetic models described the biosorption kinetics accurately, and the sorption process was found to be controlled by pore and surface diffusion for these biosorbents. Results of four-stage batch biosorber design analysis revealed that the required time for the 99 % efficiency removal of 40 mg/L N-NH₄ ⁺ from 500 L of aqueous solution were 76 and 96 min for C. indica and JOC, respectively. The Fourier transform infrared spectroscopy analysis before and after biosorption of ammonium onto C. indica and JOC revealed involvement of carboxylic and hydroxyl functional groups.     

Biosorption of Cr(III) and Cr(VI) species from aqueous solution by Cabomba caroliniana: kinetic and equilibrium study

This study reports the potential ability of non-living biomass of Cabomba caroliniana for biosorption of Cr(III) and Cr(VI) from aqueous solutions. Effects of contact time, biosorbent dosage, pH of the medium, initial concentration of metal ion and protonation of the biosorbent on heavy metal–biosorbent interactions were studied through batch sorption experiments. Cr(III) was sorbed more rapidly than Cr(VI) and the pH of the medium significantly affected the extent of biosorption of the two metal species differently. Surface titrations showed that the surface of the biosorbent is positively charged at low pH while it is negatively charged at pH higher than 4.0. Protonation of the biosorbent increased its capacity for removal of Cr(III), while decreasing that of Cr(VI). FT-IR spectra of the biosorbent confirmed the involvement of –OH groups on the biosorbent surface in the chromium removal process. Kinetic and equilibrium data showed that the sorption process of each chromium species followed pseudo second-order kinetic model and both Langmuir and Freundlich isothermal models. A possible mechanism for the biosorption of chromium species by non-living C. caroliniana is suggested.     

Typha domingensis leaf powder for decontamination of aluminium, iron, zinc and lead: Biosorption kinetics and equilibrium modeling

The present study explores the effectiveness of Typha domingensis leaf powder for simultaneous removal of aluminium, iron, zinc and lead ions from aqueous solution. Batch experiments were carried out in laboratory at room temperature and at initial ions concentrations simulating the concentrations of these cations in real wastewater samples. The sorption process was examined applying the first and second order kinetic mechanisms. The results were best described by the second order rate kinetics. The applicability of the three equilibrium isotherm models was investigated. The obtained data follow the three investigated isothermal models in the following order: Langmuir > Freundlich > Temkin, for all the studied metal ions. The infrared spectra of native and exhausted Typha leaf powder confirmed ions-biomass interactions responsible for sorption. The results showed that Typha domingensis leaf powder can easily be envisaged as a new low cost natural biosorbent for metal clean up operations in aquatic systems.     

The influence of pH on the kinetics, reversibility and mechanisms of Pb(II) sorption at the calcite-water interface

Pb(II) sorption experiments with calcite powders were conducted in suspensions equilibrated at atmospheric PCO_2(g) and ambient temperature at pH 7.3, 8.2 and 9.4. Pb fractional sorption was low at pH 7.3 and 9.4 relative to pH 8.2, and correlated well with PbCO₃⁰_(aq) speciation. Desorption experiments conducted for initial sorption times ranging from 0.5 h to 12 d reveal an almost completely reversible process at pH 8.2, attributed to the dominance of an adsorption mechanism, with slight and pronounced irreversibility at pH 7.3 and 9.4 respectively. Similarities in X-ray absorption near edge spectra (XANES) for 24 h and 12 d pH 7.3 and 9.4 sorption samples indicate no effect of initial sorption time. Results from linear combination (LC) fits of XANES spectra for samples sorbed at pH 9.4 confirm ∼75% adsorbed and ∼25% coprecipitated components. The coprecipitated fraction was attributed to the non-exchangeable metal observed in desorption experiments. At pH 7.3, ∼95% adsorbed and ∼5% coprecipitated components were obtained. A comparison of results from desorption experiments and LC-XANES alludes to an irreversibly bound adsorbed component for the pH 9.4 12 d sorption sample. Extended X-ray absorption fine structure spectroscopy (EXAFS) analysis of pH 7.3 and 9.4 12 d sorption samples confirms the presence of both adsorbed and coprecipitated metal. At pH 7.3 a first-shell Pb-O bond length of 2.38 Å is intermediate between that of adsorbed (2.34 Å) and coprecipitated (2.51 Å) Pb. At pH 9.4, two first-shell Pb-O distances at 2.35 Å and 2.51 Å were obtained, indicative of the occurrence of both adsorption and coprecipitation and a larger coprecipitated fraction relative to that at pH 7.3, consistent with LC-XANES results. We propose that the disparity in the fraction of coprecipitated metal with pH may be linked to the ability of sorbed Pb to inhibit near-surface dynamic exchange of Ca and CO₃ species, which dictates step advance and retreat. Less effective inhibition of step motion at pH 9.4, due to lower fractional sorption, combined with highest rates of dynamic exchange results in a significant fraction of coprecipitated Pb at this pH. At low pH, though fractional sorption is also low, lower rates of exchange prohibit significant coprecipitation. At pH 8.2, effective inhibition of surface processes due to higher fractional sorption and lower rates of exchange compared to pH 7.3 and 9.4 preclude detectable coprecipitation. Other factors such as changes in surface speciation and solubility of the Pb-Ca solid solution with pH may also come into play. Overall, this study presents evidence for the influence of pH on Pb sorption mechanisms, and addresses the efficiency of Pb immobilization in calcitic systems.     

Lead and nickel biosorption with a fungal biomass isolated from metal mine drainage: Box–Behnken experimental design

The Pb(II) and Ni(II) biosorption of a fungal biomass isolated from mine drainage of metal-processing industries in Balya (Bal?kesir province, Turkey) was optimized using a response surface methodology by altering parameters such as pH, initial metal concentration, contact time and biosorbent dosage. This strain was shown to be highly similar to Penicillium sp. Furthermore, zeta potential measurements and Fourier transform infrared spectroscopy were performed to understand the adsorption mechanism. A Box–Behnken design with 29 experiments was used to evaluate the interactions between independent variables. The results showed that the fungal biomass isolated from the metal mine drainage could have a significant environmental impact through the biosorption of Pb(II) and Ni(II) in waters polluted with heavy metals, particularly in the drainage from metal mines. The maximum removal values were 76 and 47 % at pH 4.5 for both Pb(II) and Ni(II), with 123 and 33 mg/L initial metal concentrations, 65 and 89 min contact times and 0.2 and 1.6 g/L biosorbent, respectively.     

Heavy metal biosorption potential of a Malaysian Rhodophyte (<Emphasis Type="Italic">Eucheuma denticulatum</Emphasis>) from aqueous solutions

Biosorption is a promising technology for the removal of heavy metals from industrial wastes and effluents. In the present study, biosorption of Pb²⁺, Cu²⁺, Fe²⁺ and Zn²⁺ onto the dried biomass of Eucheuma denticulatum (Rhodophyte) was investigated as a function of solution pH, contact time, temperature and initial metal ion concentration. The experimental data were evaluated by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The sorption isotherm data followed Langmuir and Freundlich models, and the maximum Langmuir monolayer biosorption capacity was found as 81.97, 66.23, 51.02 and 43.48 mg g^?1 for Pb²⁺, Cu²⁺, Fe²⁺ and Zn²⁺, respectively. The sorption kinetic data followed pseudo-second-order and intraparticle diffusion models. Thermodynamic study revealed feasible, spontaneous and endothermic nature of the sorption process. Fourier transform infrared analysis showed the presence of amine, aliphatic, carboxylate, carboxyl, sulfonate and ether groups in the cell wall matrix involved in metal biosorption process. A total of nine error functions were applied in order to evaluate the best-fitting models. We strongly suggest the analysis of error functions for evaluating the fitness of the isotherm and kinetic models. The present work shows that E. denticulatum can be a promising low-cost biosorbent for removal of the experimental heavy metals from aqueous solutions. Further study is warranted to evaluate its potential for the removal of heavy metals from the real environment.     

Biosorption studies on shelled Moringa oleifera Lamarck seed powder: Removal and recovery of arsenic from aqueous system

The present study explores the unexploited sorption property of the shelled Moringa oleifera seeds (SMOS) for decontamination of arsenic from water bodies. Sorption studies (batch experiments) result into the standardization of optimum conditions for removal of 60.21% As(III) and 85.60% As(V) as follows: biomass dosage (2.0 g), metal concentration (25 mg/L), contact time (60 min) and volume of the test solution (200 ml) at pH 7.5 and 2.5, respectively. The adsorption data are fitted with Langmuir isotherm. Surface area has been measured using BET surface area analyzer. Morphological changes observed in scanning electron micrograph of native and treated SMOS indicates the existence of biosorption process. Fourier transform infrared spectrometry of exhausted seed biomass highlights protein/amino acid–arsenic interactions responsible for sorption phenomenon. Regeneration has also been attempted for several cycles with a view to restore the sorbent to its original state. The sorption capacity of the regenerated biomass remained almost constant after three cycles of sorption process, suggesting that the lifetime cycle was sufficient for continuous application. The findings open up new avenues in the decontamination of arsenic using SMOS from arsenic contaminated water, as domestic and environment-friendly safe technology.     

Biosorption optimization and equilibrium isotherm of industrial dye compounds in novel strains of microscopic fungi

The aim of this study was to evaluate the biosorption capacity of selected strains of microscopic fungi. We optimized the biosorption process and used the Freundlich isotherm for three strains: H. haematococca BwIII43, K37 and T. harzianum BsIII33 to describe the biosorption equilibrium of anthraquinone dye, Alizarin Blue Black B (ABBB) and alkali lignin (AL). In optimal conditions (1 g of mycelium biomass, pH = 7.0, 28 °C) for ABBB and AL sorption, the live biomass of H. haematococca BwIII43 was characterized by a higher sorption capacity, amounting to 247.47 and 161.00 mg g^?1, respectively. The highest sorption properties toward anthraquinone dye (K _F = 19.96 mg g^?1) were shown for the biomass of H. haematococca K37. In the presence of alkali lignin, the highest sorption capacity and bond strength exhibited the biomass of H. haematococca BwIII43 (K _F = 28.20 mg g^?1, n = 3.46). Effective decolorization of ABBB and AL by the selected strains of microscopic fungi indicated that the biosorption process additionally enhanced the removal of color compounds from the solution.     

Removal of uranium(VI) from aqueous solutions using Eucalyptus citriodora distillation sludge

Adsorption and desorption of uranium(VI) from dilute aqueous solutions by Eucalyptus citriodora distillation sludge was studied in a batch mode. The potential of Eucalyptus citriodora distillation sludge to remove uranium(VI) from aqueous solutions has been investigated at different conditions of solution pH, metal ion concentrations, biosorbent dosage, biosorbent particle size, contact time and temperature. The results indicated that biosorption capacity of Eucalyptus citriodora distillation sludge was strongly affected by the medium pH, the biosorbent dose, metal ion concentrations and medium temperature. Reduction in particle size increased the biosorption capacity. Langmuir and Freundlich isotherm models were applied to biosorption data to determine the biosorption characteristics. An optimum biosorption capacity (57.75 mg/g) was achieved with pH 4.0, particle size 0.255 mm, biosorbent dose 0.5 g/100 mL and initial uranium(VI) concentration of 100 mg/L. Uranium(VI) removal by Eucalyptus citriodora distillation sludge was rapid, the equilibrium was established within 60 min and pseudo-second-order model was found to fit with the experimental data. The biosorption process decreased with an increase in the temperature indicating its exothermic nature. Pretreatments of biomass with different reagents affected its biosorption capacity. A significant increase (34 %) in biosorption capacity (83.25 mg/g) was observed with benzene treatment. Fourier-transform infra-red studies showed the involvement of carbonyl, carboxyl and amide groups in the biosorption process. The results indicated that sulfuric acid had the best effects as an eluent showing 93.24 % desorption capacity.     

Competitive sorption and desorption of cadmium and lead in paddy soils of eastern China

To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K _d) values were K _{d single} (Pb) > K _{d binary} (Pb) > K _{d single} (Cd) > K _{d binary} (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b ₁), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d _Cd*) was much greater than Pb (d _Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.     

Adsorption kinetics and intraparticulate diffusivities of Hg, As and Pb ions on unmodified and thiolated coconut fiber

As, Hg and Pb are examples of heavy metals which are present in different types of industrial effluents responsible for environmental pollution. Their removal is traditionally made by chemical precipitation, ion-exchange and so on. However, this is expensive and not completely feasible to reduce their concentrations to the levels as low as required by the environmental legislation. Biosorption is a process in which solids of natural origin are employed for binding the heavy metal. It is a promising alternative method to treat industrial effluents, mainly because of its low cost and high metal binding capacity. The kinetics was studied for biosorption experiments using coconut fiber for As (III), Hg (II) and Pb (II) ions adsorption. The specific surface area and surface charge density of the coconut fiber are 1.186×10²⁵ (m²/g) and 5.39 ×10²⁴ (meq/m²), respectively. The maximum adsorption capacity was found to be the highest for Pb (II) followed by Hg (II) and As (III). The modification of the adsorbent by thiolation affected the adsorption capacity. Equilibrium sorption was reached for the metal ions at about 60 min. The equilibrium constant and free energy of the adsorption at 30 °C were calculated. The mechanism of sorption was found to obey the particle-diffusion model. The kinetic studies showed that the sorption rates could be described by both pseudo first-order and pseudo second-order models. The pseudo second-order model showed a better fit with a rate constant value of 1.16 × 10^?4/min. for all three metal ions. Therefore, the results of this study show that coconut fiber, both modified and unmodified, is an efficient adsorbent for the removal of toxic and valuable metals from industrial effluents.     

Competitive sorption of copper and lead at the oxide-water interface: Implications for surface site density

The competitive sorption of Cu(II) and Pb(II) to colloidal hematite was investigated as a function of pH and total metal concentration. Acid–base titrations of the hematite and single-metal sorption experiments for Cu and Pb at low to medium surface coverages were used to calibrate two surface complexation models, the triple layer model, and a 2-pK basic Stern model with ion-pair formation. The surface site density was systematically varied from 2 to 20 sites/nm². Three different metal surface complexes were considered: (1) an inner-sphere metal complex; (2) an outer-sphere metal complex; and (3) an outer-sphere complex of singly hydrolyzed metal cations. Both models provided excellent fits to acid–base titration and single-metal sorption data, regardless of the surface site density used. With increasing site density, ΔpK of the stability constants for protonation reactions increased and metal surface complexes decreased steadily. The calibrated models based on different site densities were used to predict competitive sorption effects between Cu and Pb and single-metal sorption at higher total metal concentrations. Precipitation of oversaturated solid phases was included in the calculations. Best predictions of competitive sorption effects were obtained with surface site densities between 5 and 10 sites/nm². The results demonstrate that surface site density is a key parameter if surface complexation models are exposed to more complex, multicomponent environments. We conclude that competitive metal sorption experiments can be used to obtain additional information about the relevant surface site density of oxide mineral surfaces.     

Study of mango biomass (Mangifera indica L) as a cationic biosorbent

Unfertilizable fruiting buds of mango plant Mangifera Indica L, an agrowaste, is used as a biomass in this study. The efficacy of the biosorbent was tested for the removal of lead, copper, zinc and nickel metal ions using batch experiments in single and binary metal solution under controlled experimental conditions. It is found that metal sorption increases when the equilibrium metal concentration rises. At highest experimental solution concentration used (150 mg/L), the removal of metal ions were 82.76 % for lead, 76.60 % for copper, 63.35 % for zinc and 59.35 % for nickel while at lowest experimental solution concentration (25 mg/L), the removal of metal ions were 92.00% for lead, 86.84 % for copper, 83.96 % for zinc and 82.29 % for nickel. Biosorption equilibrium isotherms were plotted for metal uptake capacity (q) against residual metal concentrations (C_f) in solution. The q versus C_f sorption isotherm relationship was mathematically expressed by Langmuir and Freundlich models. The values of separation factor were between zero and one indicating favourable sorption for four tested metals on the biosorbent. The surface coverage values were approaching unity with increasing solution concentration indicating effectiveness of biosorbent under investigation. The non-living biomass of Mangifera indica L present comparable biosorption capacity for lead, copper, zinc and nickel metal ions with other types of biosorbent materials found in literature and is effective to remove metal ions from single metal solutions as well as in the presence of other co-ions with the main metal of solution.     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

Biosorption characteristics of heavy metals (Ni2+, Zn2+, Cd2+, Pb2+) from aqueous solution by Hizikia fusiformis

Heavy metal ions (Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺) were biosorbed by brown seaweed (Hizikia fusiformis), which was collected from Jeju Island of South Korea. The metal adsorption capacity of H. fusiformis improved significantly by washing with water or by base or acid treatments. The maximum sorption by NaOH-pretreated biomass was observed near a slightly acidic pH (pH 4?6) for Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺. This result suggests that the treatment of H. fusiformis biomass with NaOH helped increase the functional forms of carboxylate ester units. Kinetic data showed that the biosorption occurred rapidly during the first 60 min, and most of the heavy metals were bound to the seaweed within 180 min. The maximum metal adsorption capacities assumed by a Langmuir model were on the order of Pb²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺. Equilibrium adsorption data for the heavy metal ions could fit well in the Langmuir model with regression coefficients R ² > 0.97.     

Response surface methodology for lead biosorption on Aspergillus terreus

A central composite face-centered design was used to study and to optimize lead biosorption from aqueous solution on Aspergillus terreus biomass. Four factors such as stirring speed, temperature, solution pH and biomass dose at different levels were studied.The hierarchical quadratic model were established by adding replicates at the central point and axial points to the initial full factorial design (2⁴). The percentage removal of lead was affected by biomass dose, pH, and interactions between pH and biomass dose, pH and stirring speed, pH and temperature. The hierarchical quadratic model described adequately the response surface based on the adjusted determination coefficient (R² _Adj= 0.97) and the adequate precision ratio (42.21). According to this model, the optimal conditions to remove lead completely from aqueous solutions (at initial lead concentration of 50 mg/L and solutions of 100 mL) with Aspergillus terreus were at pH 5.2, 50 °C, stirring speed of 102/min and a biomass dose of 139 mg.The response surface methodology can be used to determine the optimal conditions for metal adsorption on several adsorbents. In addition, results reported in this research demonstrated the feasibility of employing A. terreus as biosorbent for lead removal.     

Surface modification of <Emphasis Type="Italic">Nizimuddinia zanardini</Emphasis> and <Emphasis Type="Italic">Stoechospermum marginatum</Emphasis> using 4-phenyl-3-thiosemicarbazide to improve heavy metals biosorption from water

Surface modification of two algal biomasses, Nizimuddinia zanardini and Stoechospermum marginatum, using 4-phenyl-3-thiosemicarbazide ligand was performed to investigate the consequences on the adsorption of heavy metals from aqueous solution. Stabilization of amino group of 4-phenyl-3-thiosemicarbazide on the surface of biomasses was confirmed using Fourier transform infrared spectroscopy. Chemical modification was found to exert significant positive effects on biosorption. Adsorption capacities for Pb(II), Cd(II) and Cr(VI) using modified N. zanardini were observed to be 19.3, 16.75 and 15.75 mg/g, respectively, compared to 17.48, 14.18 and 11.85 mg/g for raw N. zanardini biomass. Also, adsorption of Pb(II), Cd(II) and Cr(VI) by the modified S. Marginatum was found to be 17.54, 15.62 and 14.77 mg/g, respectively, in comparison with that of the raw biomass which were 16.86, 12.9 and 11.2 mg/g. The obtained results of the equilibrium adsorption were studied through different isotherm models of Langmuir, Freundlich and Temkin, where the Langmuir model was observed to agree well with the results. Prevalent kinetic models including pseudo-second order and intra-particle diffusion were applied, and the pseudo-second order was found to describe the adsorption kinetics data adequately. Intra-particle model was also utilized in order to show penetration of metal ions, where it was realized that the biosorption took place in two or three steps including film diffusion, molecular diffusion and chemical reaction.     

Effects of pH on isotherm modeling and cation competition for Cd(II) and Cu(II) biosorption on Myriophyllum spicatum from aqueous solutions

The biosorption characteristics of Cd(II) and Cu(II) ions from aqueous solutions obtained using submerged aquatic plant (Myriophyllum spicatum) biomass were investigated in terms of equilibrium, kinetics, thermodynamics, and cation competition. Langmuir and Freundlich models were applied to describe the biosorption isotherm of metal ions by M. spicatum biomass and isotherm constants considering the most important parameter, pH. The variation of sorption isotherm constants showed pH dependence. The Langmuir and Freundlich models fitted the equilibrium data well. The maximum biosorption capacity (q _m) of M. spicatum biomass was determined to be 29.07 mg/g for the Cd(II) ion at pH 5.0 and 12.12 mg/g for the Cu(II) ion at pH 6.0. Chi square analysis showed that the Freundlich model fitted the equilibrium data better than the Langmuir isotherm. Competition of Cd(II) and Cu(II) in a binary solution showed that the Langmuir monolayer capacity of Cd(II) decreased from 29.07 mg/g with only Cd(II) in solution to 12.02 mg/g in the presence of Cu(II). Kinetics results showed that the biosorption processes of both metal ions followed the pseudo-second-order kinetics well. The calculated thermodynamic parameters (?G ⁰, ?H ⁰, and ?S ⁰) showed that biosorption of Cd(II) and Cu(II) ions onto M. spicatum biomass was feasible, spontaneous, and endothermic in nature. Fourier transform infrared spectroscopy spectrum analysis revealed that Cd(II) and Cu(II) sorption was mainly ascribed to carboxyl, hydroxyl, amine, and C–N groups in M. spicatum.     

Sorption and distribution of adsorbed metals in three soils of India

The mobility and bioavailability of heavy metals depends on the metal retention capacity of soil and also on the geochemical phases with which metals are associated. Laboratory batch experiments were carried out to study the sorption and distribution of Cd, Ni and Pb in 3 soils differing in their physicochemical properties from India: Oxyaquic Haplustalf (SL1), Typic Haplustalf (SL2) and Typic Haplustert (SL3). The heavy metal adsorption was studied by isotherms and the distribution coefficient (K_D) for each metal was obtained from the linear regressions of the concentration of metal remaining in equilibrium solution and the amount adsorbed. In general, the sorption capacity for all the metals decreased in the order: SL3>SL2>SL1. Among metals, the sorption capacity in all the soils decreased in the order: Pb>>Ni>Cd. Distribution of sorbed metals at various equilibrating concentrations was studied by sequential extraction. Results showed significant differences in the distribution of metals in these soils. At higher additions (such as 200 μM l⁻¹) most of the metals were extracted in their more mobile fractions, exchangeable and/or inorganic in contrast to their original partitioning in soils, where they were preferentially associated with the less mobile residual fraction. Largest percentages of metals extracted in the exchangeable fraction corresponded to those soil–metal systems with smaller K_D values, e.g. Cd, Ni and Pb in SL1 and Cd and Ni in SL2. In neutral and alkaline soils (SL2, pH=7.1, and SL3, pH=8.6) Pb was predominantly extracted from the inorganic fractions and this corresponded to higher K_D values for Pb in these soils. The predominance of metals associated with the exchangeable fraction together with low K_D values indicates higher mobility of metals retained in the acidic soil (SL1, pH=5.2) compared with the others.