Description of two-metal biosorption equilibria by Langmuir-type models

A biosorbent prepared from Ascophyllum nodosum seaweed biomass, FCAN2, was examined for its sorption capacity. Equilibrium batch sorption studies were performed using two-matal systems containing either (Cu + Zn), (Cu + Cd), or (Zn + Cd). In the evaluation of the two-metal sorption system performance, simple isotherm curves had to be replaced by three-dimensional sorption isotherm surfaces. In order to describe the isotherm surfaces mathematically, three Langmuir-type models were evaluated. The apparent one-parameter Langmuir constant (b) was used to quantify FCAN2 "affinity" for one metal in the presence of another one. The uptake of Zn decreased drastically when Cu or Cd were present. The uptake of Cd wasmuch more sensitive to the presence of Cu than to that of Zn. The presence of Cd and Zn alter the "affinity" of FCAN2 for Cu the least at high Cu equilibrium concentrations. The mathematical model of the two-metal sorption system enabled quantitative estimation of one-metal (bio)sorption inhibition due to the influence of a second metal. (c) 1995 John Wiley & Sons Inc.     

Two metal biosorption of chromium and copper by Ca-loaded Laminaria japonica biomass

Cu and Cr sorption capacities of Ca-loaded Laminaria japonica biomass were studied using an equilibrium methodology and evaluation of the sorption performance, and modeling in a two-metal system was carried out with a modified multi-component Langmuir isotherm. The maximum Cu and Cr uptakes calculated from the Langmuir isotherm were 1.59 mmol/g (10.1 wt.%) and 1.81 mmol/g (9.4 wt.%) at pH 4.5, respectively. The desorption efficiency of the Cr-sorbed L. japonica was approximately 5% for 8 h in the 0.1 N HNO₃ solution, while that of Cu-sorbed L. japonica was more than 99% in the 0.1 N HNO₃ solution. The modified Langmuir model gave the following affinity correlated coefficients: 1.12 for Cu and 7.31 for Cr at pH 4.5. The interference of Cr with Cu biosorptive uptake was assessed by ‘cutting’ the three dimensional uptake isotherm surfaces at constant second-metal final concentrations. Equimolar final equilibrium concentrations of Cu and Cr of 1 mM at pH 4.5 reduced Cu and Cr uptakes by 75.5 and 11.0%, respectively.     

废啤酒酵母吸附水溶液中Cu2+的性能及机理研究

用废啤酒酵母吸附水溶液中Cu2+,考察了溶液pH值、Cu2+浓度和吸附时间对Cu2+吸附的影响。结果表明：废啤酒酵母吸附Cu2+在4-6个小时内达到吸附平衡,酸性条件利于吸附,以pH为5时最佳,吸附等温曲线符合Langmuir模式。用电位滴定及FTIR分析的方法确定生物吸附剂主要含有磺酸基、羧基及氨基等功能团。生物吸附剂对Cu2+的吸附以单分子层的化学吸附为主,功能团在不同的pH条件下呈现不同的电离性能,在吸附过程中发挥重要作用。     

Uptake and recovery of gold ions from electroplating wastes using eggshell membrane.

The animal byproduct, hen eggshell membrane (ESM), was evaluated for its ability to sorb gold ions (dicyanoaurate(I) and tetrachloroaurate(III)) from solutions and electroplating wastewater. The gold uptake was dependent on pH, temperature and co-ions present in the solutions, with pH 3.0 being the optimum value. The equilibrium data followed the Langmuir isotherm model with maximum capacities of 147 mg Au(I)/g dry weight and 618 mg Au(III)/g, respectively. Desorption of sorbed gold(I) with 0.1 mol/l NaOH resulted in no changes of the biosorbent gold uptake capacity through five consecutive sorption/desorption cycles. In column experiments, selective recovery of gold from electroplating wastewater containing various metal ions was noted. The affinity of metal sorption was in the order Au > Ag > Co > Cu > Pb > Ni > Zn.     

Biosorption of Cu2+, Cd2+, Pb2+, and Zn2+ using dried marine green macroalga Caulerpa lentillifera

The sorption of Cu2+, Cd2+, Pb2+, and Zn2+ by a dried green macroalga Caulerpa lentillifera was investigated. The removal efficiency increased with pH. The analysis with FT-IR indicated that possible functional groups involved in metal sorption by this alga were O-H bending, N-H bending, N-H stretching, C-N stretching, C-O, SO stretching, and S-O stretching. The sorption of all metal ions rapidly reached equilibrium within 20min. The sorption kinetics of these metals were governed by external mass transfer and intraparticle diffusion processes. The sorption isotherm followed the Langmuir isotherm where the maximum sorption capacities was Pb2+>Cu2+>Cd2+>Zn2+.     

Copper inclusion in cellulose using sodium d-gluconate complexes

Copper containing cellulose material is of growing interest, e.g. offering alternative in the field of antimicrobials. Solutions of copper d-gluconate complexes (Cu(2+)-DGL) were used to introduce copper ions into a swollen cellulosic matrix. A ligand exchange mechanism forms the chemical basis of the sorption process. Copper sorption in cellulose was studied in the range between pH 6 and 13. An estimate for the complex stabilities of the Cu-cellulose system could be derived from the calculated species distribution of the different Cu(2+)-DGL complexes present. Spectrophotometry and cyclic voltammetry of Cu(2+)-DGL complex solution were used to confirm the presence of different species participating in the ligand exchange reaction. The pH dependent uptake of Cu(2+) ions in the cellulose matrix can be explained on the basis of the relative stabilities of Cu(2+)-DGL complex vs. Cu(2+)-cellulose complexes. In comparison to pH 10, higher copper content was observed at pH 6 and 13. Copper content was limited by carboxyl content of cellulosic materials, thus in analogy to the structure of Cu(2+)-DGL complexes participation of the carboxyl group as complex forming site is proposed. At high Cu(2+)-concentration and longer time of immersion in the copper complex solutions formation of solid deposits was observed on the surface of the treated fibres.     

Suspended particulate oxides and organic matter interactions in trace metal sorption reactions in a small urban river

The relative scavenging abilities of suspended particulate oxides (SPOX), and organic matter (SPOM) for Cd, Zn and Cu were evaluated in a small, anthropogenically influenced river. In addition, the factor most important in influencing the sorption density (A_d: metal concentration associated with a given phase divided by the concentration of that geochemical phase in the suspended particulate pool) of each metal to SPOX and SPOM were identified through multiple linear regression analyses from the suite of: pH, temperature, dissolved metal concentration, and the concentration of the other particulate fraction. Results indicate that SPOX-SPOM interactions do occur in trace metal complexation reactions; and interactions are both phase and cation specific. Fe oxides are able to outcompete discrete organic binding sites for Cu and Zn as a relative decrease in the amount of these two cations sorbed to organic matter was observed with increasing particulate Fe oxides. SPOM concentration was identified as being most important in influencing Cu sorption densities associated with the SPOX fraction. Organic matter — oxide complexes are postulated to occur that enhance oxide sorption of Cu such that relatively more Cu is sorbed to particulate oxides with increasing particulate organic matter concentrations. Dissolved concentrations of Cd and Zn were found to be most important in influencing the sorption densities for these two metals associated with the oxides fraction. The sorption behaviour appears to follow Freundlich isotherm behaviour where the amount sorbed is a function of the dissolved concentration.     

Removal and recovery of Cu(II) and Zn(II) using immobilized Mentha arvensis distillation waste biomass

The potential use of the immobilized Mentha arvensis distillation waste (IMADW) biomass for removal and recovery of Cu(II) and Zn(II) from aqueous was evaluated in the present study. Biosorption capacity of Cu(II) and Zn(II) on IMADW increased with increase in pH reaching a maximum at 5 for Cu(II) and 6 for Zn(II). The equilibrium sorption data agreed well with Langmuir isotherm model and pseudo-second-order kinetic model in batch mode. Cu(II) and Zn(II) uptake by IMADW was best described by pseudo-first-order kinetic model in continuous mode. Maximum Cu(II) and Zn(II) uptake by IMADW was 104.48 and 107.75 mg/g, respectively. Fourier Transform Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were also carried out to investigate functional groups and surface changes of biomass. The results showed that IMADW biomass is a potential biomaterial to remove Cu(II) and Zn(II) ions with a high biosorption capacity from aqueous solutions.     

Kinetic and Equilibrium Studies of Cr(VI) Biosorption by Dead <Emphasis Type="Italic">Bacillus licheniformis</Emphasis> Biomass

Many studies have been carried out on the biosorption capacity of different kinds of biomass. However, reports on the kinetic and equilibrium study of the biosorption process are limited. In our experiments, the removal of Cr(VI) from aqueous solution was investigated in a batch system by sorption on the dead cells of Bacillus licheniformis isolated from metal-polluted soils. Equilibrium and kinetic experiments were performed at various initial metal concentrations, pH, contact time, and temperatures. The biomass exhibited the highest Cr(VI) uptake capacity at 50°C, pH 2.5 and with the initial Cr(VI) concentration of 300 mg/g. The Langmuir and Freundlich models were considered to identify the isotherm that could better describe the equilibrium adsorption of Cr(VI) onto biomass. The Langmuir model fitted our experimental data better than the Freundlich model. The suitability of the pseudo first-order and pseudo second-order kinetic models for the sorption of Cr(VI) onto Bacillus licheniformis was also discussed. It is better to apply the pseudo second-kinetic model to describe the sorption system.     

Biosorption of fluoride from aqueous phase onto algal Spirogyra IO1 and evaluation of adsorption kinetics

Non-viable algal Spirogyra IO1 was studied for its fluoride sorption potential in batch studies. The results demonstrated the ability of the biosorbent for fluoride removal. The sorption interaction of fluoride on to non-viable algal species obeyed the pseudo-first-order rate equation. The intraparticle diffusion of fluoride molecules within the Spirogyra was identified to be the rate-limiting step. It was also found that the adsorption isotherm followed the rearranged Langmuir isotherm adsorption model. Fluoride sorption was dependent on the aqueous phase pH and the fluoride uptake was greater at lower pH.     

Concurrent sorption of Zn(II), Cu(II) and Co(II) by Oscillatoria angustissima as a function of pH in binary and ternary metal solutions

This paper reports biosorption of Zn(II), Cu(II) and Co(II) onto O. angustissima biomass from single, binary and ternary metal solutions, as a function of pH and metal concentrations via Central Composite Design generated by statistical software package Design Expert 6.0. The experimental design revealed that metal interactions could be best studied at lower pH range i.e. 4.0-5.0, which facilitates adequate availability of all the metal ions. The sorption capacities for single metal decreased in the order Zn(II)>Co(II)>Cu(II). In absence of any interfering metals, at pH 4.0 and an initial metal concentration of 0.5 mM in the solution, the adsorption capacities were 0.33 mmol/g Zn(II), 0.26 mmol/g Co(II) and 0.12 mmol/g Cu(II). In a binary system, copper inhibited both Zn(II) and Co(II) sorption but the extent of inhibition of former was greater than the latter; sorption values being 0.14 mmol/g Zn(II) and 0.27 mmol/g Co(II) at initial Zn(II) and Co(II) concentration of 1.5 mM each, pH 4.0 and 1mM Cu(II) as the interfering metal. Zn(II) and Co(II) were equally antagonistic to each others sorption; Zn(II) and Co(II) sorption being 0.23 and 0.24 mmol/g, respectively, at initial metal concentration of 1.5 mM each, pH 4.0 and 1mM interfering metal concentration. In contrast, Cu(II) sorption remained almost unaffected at lower concentrations of the competing metals. Thus, in binary system inhibition dominance observed was Cu(II)>Zn(II), Cu(II)>Co(II) and Zn(II) approximately Co(II), due to this the biosorbent exhibited net preference/affinity for Cu(II) sorption over Zn(II) or Co(II). Hence, the affinity series showed a trend of Cu(II)>Co(II)>Zn(II). In a ternary system, increasing Co(II) concentration exhibited protection against the inhibitory effect of Cu(II) on Zn(II) sorption. On the other hand, the inhibitory effect of Zn(II) and Cu(II) on Co(II) sorption was additive. The model equation for metal interactions was found to be valid within the design space.     

Ion exchange during heavy metal bio-sorption from aqueous solution by dried biomass of macrophytes

In this study, potentials of oven dried biomass of Eichhornia crassipes, Valisneria spiralis and Pistia stratiotes, were examined in terms of their heavy metal (Cd, Ni, Zn, Cu, Cr and Pb) sorption capacity, from individual-metal and multi-metal aqueous solutions at pH 6.0+/-0.1 (a popular pH of industrial effluent). V. spiralis was the most and E. crassipes was the least efficient for removal of all the metals. Cd, Pb and Zn were efficiently removed by all the three biomass. Cd was removed up to 98% by V. spiralis. Sorption data for Cr, Ni and Cd fitted better to Langmuir isotherm equation, while, the sorption data for Pb, Zn and Cu fitted better to Freundlich isotherm equation. In general, the presence of other metal ions did not influence significantly the targeted metal sorption capacity of the test plant biomasses. Ion exchange was proven the main mechanism involved in bio-sorption and there was a strong ionic balance between adsorbed (H(+) and M(2+)) to the released ions (Na(+) and K(+)) to and from the biomass. No significant difference was observed in the metal exchanged amount, by doubling of metal concentration (15-30 mg/l) in the solution and employing individual-metal and multi-metal solutions.     

Kinetic modeling for the biosorption of copper by pretreated Aspergillus niger biomass

In this present work, a kinetic model for biosorption of copper was developed considering the possibility of different forms of functional groups being present on the surface of the biomass prepared from Aspergillus niger. Results showed that metal uptake by A. niger was a mass transfer driven process, requiring only 30min to achieve 70% adsorption efficiency. Copper sorption by A. niger was influenced by the biomass dose, initial metal ion concentration, and pH of the solution. The Langmuir and Freundlich adsorption isotherms were used to describe the behavior of the system at different pH. The retention capacity of the biomass was determined at pH 6.0 to be equal to 23.62mg/g of biomass. The pretreatment with formalin improved the uptake of metal ion.     

Micronutrient Cation Sorption by Roots and Uptake by Plants

The sorption of ferric iron, copper, zinc and manganese by wheatseedling roots and by discs of cellulose filter paper was measured.The magnitude of sorption at pH 5-0 was Fe(III) > Cu(II)> Zn(II) > Mn(II). Sorption of Cu(II), Zn(II) and Mn(II)increased with increasing pH whilst sorption of Fe(III) decreased.The patterns of sorption are discussed in the light of our knowledgeof the hydrolysis of the metal ions. It is suggested that metalsadsorbed on root surfaces may be remobilized by organic ligandswhich leak from the root cells. Where an external liquid diffusionpath away from the root does not exist, soluble metal ligandcomplexes might accumulate in the water free space and superficialwater film of the root, thus facilitating their uptake intoroot cells and translocation within the plant. Under such conditionsthe amounts of metal translocated to the shoots of wheat seedlingsare shown to be related to the amounts of metal adsorbed bytheir roots. Key words: Adsorption, Micronutrients, Roots     

The kinetics and mechanism of lead (II) biosorptionby powderized Rhizopus oligosporus

The kinetics and mechanism of lead biosorption by powderized Rhizopus oligosporus were studied using shake flask experiment. The optimum biomass concentration and initial solution pH for lead sorption at initial lead concentrations ranging from 50–200 mg/l was obtained at 0.5 g/l and pH5, respectively. In term of the ratio of initial lead concentration to biomass concentration ratio, the highest lead adsorption was obtained at 750 mg/g which gave the maximum lead uptake capacity of 126 mg/g. The experimental data of lead sorption by R.oligosporus fitted well to the Langmuir sorption isotherm model, indicating that the sorption was similar to that for an ion-exchange resin. This means that the sorption is a single layer metal adsorption that occurred as a molecular surface coverage. This assumption was confirmed by the examination of lead sorption using transmission electron microscope and energy dispersive X-ray analysis, which showed that during sorption most of the lead was adsorbed on the surface of cell.     

Removal of chromium by mucilaginous seeds of Ocimum basilicum

Polysaccharides bound to bacteria or in isolated form have been shown to bind heavy metals. A limitation of this technology can be overcome by immobilization. In view of this Ocimum basilicum seeds which swell upon wetting could serve as natural immobilized source of agriculturally-based polysaccharides. The seeds consist of an inner hard core and a pectinous fibrillar outer layer. Pretreating the seeds with acid, alkali, periodate or boiling in water was found to alter the metal binding capacity. Of the various treatments given, seeds boiled in water were found to be superior in terms of mechanical stability and exhibited fairly optimal Cr(VI) uptake kinetics. The maximum adsorption capacity as calculated from the Langmuir isotherm was 205 mg Cr/g dry seeds. Biosorption of Cr(VI) was found to be pH dependent with maximum uptake at pH 1.5 wherein sorption was not affected by the presence of other metal ions such as Cd(2+), Cu(2+), Ca(2+) and Na(+). Seeds were used in a packed bed reactor for the continuous removal of Cr(VI). Thus O. basilicum seeds may have application as a potential bioresource in tropical countries such as India where they are widely available.     

Removal of thorium from simulated acid process streams by fungal biomass

Biomass from several fungal species removed thorium from solution in 1M HNO(3), pH 0-1. Thorium uptake was saturable with increasing thorium concentration, although the equilibria did not correspond to a simple ad sorption isotherm. Thorium uptake was altered by the biomass concentration, the uptake per unit biomass being reduced at high biomass concentrations. The presence of Al(3+) and Fe(3+) only slightly inhibited uptake of thorium while Ca(2+), Mg(2+), and Na(+) had no effect. Thus fungal biomass appears capable of removing thorium from solution under chemical conditions existing in acid waste liquors. Thorium uptake was increased by pretreatment using detergent and also, in the case of filamentous fungi, varied with the culture conditions, which implies that the thorium uptake characteristics of fungal biomass are able to be manipulated by these or similar means for optimum performance.     

Equilibrium of Cu(II) and Ni(II) biosorption by marine alga Sargassum filipendula in a dynamic system: competitiveness and selectivity

The study focuses on the equilibrium of dynamic biosorption in single and binary systems containing Cu(II) and Ni(II) ions using Sargassum filipendula (a marine alga). The experiments were performed in fixed-bed columns with both single-component and bi-component metal solutions (using different molar concentrations). Experimental data were fitted with different equilibrium models such as Langmuir, Langmuir with inhibition, Jain and Snowyink and Langmuir-Freundlich equations. The biosorption of pure metal ions in solution presented adequate capacities both for Cu(II) and Ni(II). In binary solutions the preferential sorption of Cu(II) over Ni(II) was demonstrated by the displacement of Ni(II) (marked overshoot on the breakthrough curves).     

Root-zone modeling of heavy metal uptake and leaching in the presence of organic ligands

We present a mechanistic model which describes root uptake and leaching of heavy metals in the plant root zone, accounting for solution- and surface-complexation, (kinetic) mineral dissolution, heavy metal diffusion towards the root, root uptake, root exudation, ligand degradation and convective-dispersive transport of the soluble species. The model was used to simulate the influence of EDTA addition on Cu transport and plant uptake and the effect of oxalate exudation by roots on Cu transport and bioavailability using parameter values from the literature. In the simulations we assumed that free Cu²⁺ is the bioavailable form. Under slightly acidic conditions (pH 6) the model predicted that EDTA stabilizes Cu while at a slightly alkaline pH (pH 7.5), EDTA mobilizes Cu. The addition of EDTA approximately halved the cumulative Cu uptake after 360 days at pH 4.5, and reduced the uptake by a factor of 100 and 1000 at pH 6 and 7.5, respectively. Although the total dissolved concentration was increased, plant uptake was reduced by the formation of bio-inavailable complexes. The exudation of oxalate resulted in a decrease of the Cu concentration breaking through below the root zone, due to sorption of Cu-oxalate. In the presence of dissolved organic carbon (DOC), the exudation of oxalate increased Cu leaching considerably at pH 6 and 7.5. In the absence of DOC, the exudation of oxalate reduced Cu uptake due to the formation and adsorption of Cu-oxalate on goethite surface sites. Exudation of oxalate in the presence of DOC resulted in a further decrease of Cu uptake. Oxalate gradually takes over from DOC in binding Cu due to simultaneous production of oxalate and leaching of DOC. The simulations show that addition or exudation of ligands does not necessarily increase the solubility, transport and bioavailability of metals. Depending on the conditions (mainly the pH), also reduced transport and uptake can be observed, either by formation of ternary surface complexes or reduction of free metal concentration. The model can be easily extended to include further processes.