Immobilization of blue green microalgae on loofa sponge to biosorb cadmium in repeated shake flask batch and continuous flow fixed bed column reactor system

Summary An indigenous strain of blue green microalga, Synechococcus sp., isolated from wastewater, was immobilized onto loofa sponge discs and investigated as a potential biosorbent for the removal of cadmium from aqueous solutions. Immobilization has enhanced the sorption of cadmium and an increase of biosorption (21%) at equilibrium was noted as compared to free biomass. The kinetics of cadmium biosorption was extremely rapid, with (96%) of adsorption within the first 5 min and equilibrium reached at 15 min. Increasing initial pH or initial cadmium concentration resulted in an increase in cadmium uptake. The maximum biosorption capacity of free and loofa immobilized biomass of Synechococcus sp. was found to be 47.73 and 57.76 mg g⁻¹ biomass respectively. The biosorption equilibrium was well described by Langmuir adsorption isotherm model. The biosorbed cadmium was desorbed by washing the immobilized biomass with dilute HCl (0.1 M) and desorbed biomass was reused in five biosorption–desorption cycles without an apparent decrease in its metal biosorption capacity. The metal removing capacity of loofa immobilized biomass was also tested in a continuous flow fixed-bed column bioreactor and was found to be highly effective in removing cadmium from aqueous solution. The results suggested that the loofa sponge-immobilized biomass of Synechococcus sp. could be used as a biosorbent for an efficient removal of heavy metal ions from aqueous solution.     

Cadmium biosorption by <Emphasis Type="Italic">Bacillus</Emphasis><Emphasis Type="Italic"> circulans</Emphasis> strain EB1

Summary A heavy metal resistant bacterium, Bacillus circulans strain EB1 showed a high cadmium biosorption capacity coupled with a high tolerance to this metal when grown in its presence. Bacillus circulans EB1 cells grown in the presence of 28.1 mg cadmium/l were capable of removing cadmium with a specific biosorption capacity of 5.8 mg Cd/g dry wt biomass in the first 8 h. When the cells were pre-conditioned with low concentrations of cadmium in pre-grown medium, the uptake was increased to 6.7 mg Cd/g dry wt biomass. The maximum uptake of␣cadmium was during mid-logarithmic phase of growth. The resting cells (both wet and dry) of EB1 were also able to biosorb cadmium. Specific biosorption capacities of wet and dry biomass were 9.8 and 26.5 mg Cd/g dry wt biomass, respectively. Maximum cadmium removals by both wet and dry cells were at pH 7.0. The results showed that the cadmium removal capacity of resting cells was markedly higher than that of growing cells. Since both growing and resting cells had a high biosorption capacity for cadmium, EB1 cells could serve as an excellent biosorbent for removal of cadmium from natural environments.     

Cadmium biosorption by Saccharomyces cerevisiae

Cadmium uptake by nonliving and resting cells of Saccharomyces cerevisiae obtained from aerobic or anaerobic cultures from pure cadmium-bearing solutions was examined. The highest cadmium uptake exceeding 70 mg Cd/g was observed with aerobic baker's yeast biomass from the exponential growth phase. Nearly linear sorption isotherms featured by higher sorbing resting cells together with metal deposits localized exclusively in vacuoles indicate the possibility of a different metal-sequestering mechanism when compared to dry nonliving yeasts which did not usually accumulate more than 20 mg Cd/g. The uptake of cadmium was relatively fast, 75% of the sorption completed in less than 5 min. (c) 1993 Wiley & Sons, Inc.     

Biosorption of Cd, Zn and Cu by Sargassum sp. waste biomass

Biosorption is becoming an important component in the integrated approach to the treatment of aqueous effluents. The economics of biomass technical applications are improved by using waste biomass instead of purposely-produced biomass. Biomass derived from an alginate extraction industry - Sargassum sp. - was examined for its ability to function as a biosorbent for metals such as cadmium, zinc and copper. For use in column applications, biomass should be immobilized. To the algae reinforcement, the biomass was embedded in polyethleneimine (PEI), followed by glutaraldehyde crosslinking. Equilibrium Zn and Cu isotherms were analysed using the immobilization ratio that showed the best Cd performance. Either Freundlich or Langmuir models can describe the passive biosorption equilibrium of cadmium, zinc and cooper. The preference for this series of metals by the biomass was found to be Cd > Zn > Cu, with maximum uptake values of 157.8, 118.5 and 77.4 mg/g dry weight biomass for Cd, Zn and Cu. respectively. The metal binding capacity by non-living biomass is an important quality for industrial use.     

Biosorption of toxic metal ions by alkali-extracted biomass of a marine cyanobacterium,Phormidium valderianum BDU 30501

Alkali-extracted biomass of Phormidium valderianum BDU 30501, a marine filamentous, non-heterocystous cyanobacterium adsorbed more than 90% of cadmium ions from solutions containing 0.1–40mM. Cadmium binding accounted up to 18% of biomass weight (w/w). The algal biosorbent was also efficient is sequestering metal ions (Cd²+, Co²+, Cu²+, Ni²+) from a mixture. Biosorbent placed in dialysis tubing could concentrate Cd2+ (50–65%) from 1l solution (10 and 100ppm) at equilibrium. Biosorbent immobilized in polyvinyl foam also removed cadmium and cobalt efficiently, but required longer contact times (24h). Most of the bound metal ions (> 80%) could be desorbed with 0.1M HCl or EDTA, while other reagents were less efficient in the order: H2SO4 > NH4Cl > CaCl2 > Na_{2SO 4} > KSCN > KCl > NH_4OH > NaHCO₃. The regenerated biosorbent retained 80% of the initial binding capacity for Cd2+ and 50% binding capacity for Co2+ up to three cycles of reuse. Infrared spectra of the biosorbent preparation suggested carboxyl groups to be the primary sites for metal binding.     

Biosorption of lead and nickel by biomass of marine algae

Screening tests of different marine algae biomas types revealed a high passive biosorptive uptake of lead up to 270 mg Pb/g of biomass in some brown marine algae. Members of the order Fucales perfomed particularly well in this descending sequence: Fucus > Ascophyllum > Sargassum. Although decreasing the swelling of wetted biomass particles, their reinforcement by crosslinking may significantly affect the biosorption performance. Lead uptakes up to 370 mg Pb/g were observed in crosslinked Fucus vesiculosus and Ascophyllum nodosum. At low equilibrium residual concentrations of lead in solution, however, ion exchange resin Amberlite IR-120 had a higher lead uptake than the biosorbent materials. An order-of-magnitude lower uptake of nickel was observed in all of the sorbent materials examined. (c) 1994 John Wiley & Sons, Inc.     

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.     

Cadmium removal in a biosorption column

New biosorbent material derived from a ubiquitous brown marine alga Ascophyllum nodosum has been examined in packed-bed flow-through sorption columns. It effectively removed 10 mg/L of cadmium down to 1.5 ppb levels in the effluent, representing 99.985% removal. The experimental methodology used was based on the early Bohart and Adams sorption model, resulting in quantitative determination of the characteristic process parameters which can be used for performance comparison and process design. An average metal loading of the biosorbent (N(0)) determined was 30 mg Cd/g, corresponding closely to that observed for the batch equilibrium metal concentration of 10 mg Cd/L. The critical bed depth (D(min)) for the potable water effluent quality standard (0.005 mgg Cd/L) varied with the column feed flow rate (2.4 to 9.6 L/h . cm(2)) from 20 to 50 cm. The sorption column mass transfer and dispersion coefficients were determined, which are also required for solving the sorption model equations. (c) 1994 John Wiley & Sons, Inc.     

Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass

Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.     

Metal biosorption equilibria in a ternary system

Equilibrium metal uptake performance of a biosorbent prepared from Ascophyllum nodosum seaweed biomass was studied using aqueous solutions containing copper, cadmium, and zinc ions in binary and ternary mixtures. Triangular equilibrium diagrams can graphically represent all the ternary equilibrium sorption data. Application of the multicomponent Langmuir model to describe the three-metal system revealed its nonideal characteristics, whereby the value of apparent dissociation constants for the respective metals differed for each system. This restricted the prediction of the ternary equilibria from the binary systems. However, some predictions of the ternary system behavior from the model were consistent with experimental data and with conclusions postulated from the three possible binary subsystems. (c) 1996 John Wiley & Sons, Inc.     

The recovery of heavy metals using encapsulated microbial cells

We prepared capsules containingSaccharomyces cerevisiae andZoogloea ramigera cells for the removal of lead (II) and cadmium ions. Microbial cells were encapsulated and cultured in the growth medium. TheS. cerevisiae cells grown in the capsule did not leak through the capsule membrane. The dried cell density reached to 250 g/l on the basis of the inner volume of the 2.0 mm diameter capsule after 36 hour cultivation. The dry whole cell exopolymer density of encapsulatedZ. ramigera reached to 200 g/L. The capsule was crosslinked with triethylene tetramine and glutaric dialdehyde solutions. The cadmium uptake of encapsulated whole cell exopolymer ofZ. ramigera was 55 mg Cd/g biosorbent. The adsorption line followed well Langmuir isotherm. The lead uptake of the encapsulatedS. cerevisiae was about 30 mg Pb/g biomass. The optimum pH of the lead uptake using encapsulatedS. cerevisiae was found to be 6. Freundlich model showed a little better fit to the adsorption data than Langmuir model. 95 percent of the lead adsorbed on the encapsulated biosorbents was desorbed by the 1 M HCl solution. The capsule was reused 50 batches without loosing the metal uptake capacity. And the mechanical strength of the crosslinked capsule was retained after 50 trials.     

Biosorption of lead, cadmium, and zinc by Citrobacter strain MCM B-181: characterization studies

The biosorption process for removal of lead, cadmium, and zinc by Citrobacter strain MCM B-181, a laboratory isolate, was characterized. Effects of environmental factors and growth conditions on metal uptake capacity were studied. Pretreatment of biomass with chemical agents increased cadmium sorption efficiency; however, there was no significant enhancement in lead and zinc sorption capacity. Metal sorption by Citrobacter strain MCM B-181 was found to be influenced by the pH of the solution, initial metal concentration, biomass concentration, and type of growth medium. The metal sorption process was not affected by the age of the culture or change in temperature. Equilibrium metal sorption was found to fit the Langmuir adsorption model. Kinetic studies showed that metal uptake by Citrobacter strain MCM B-181 was a fast process, requiring <20 min to achieve >90% adsorption efficiency. The presence of cations reduced lead, zinc, and cadmium sorption to the extent of 11. 8%, 84.3%, and 33.4%, respectively. When biomass was exposed to multimetal solutions, metals were adsorbed in the order Co2+ < Ni2+ < Cd2+ < Cu2+ < Zn2+ < Pb2+. Among various anions tested, only phosphate and citrate were found to hamper metal sorption capacity of cells. Biosorbent beads prepared by immobilizing the Citrobacter biomass in polysulfone matrix exhibited high metal loading capacities. A new mathematical model used for batch kinetic studies was found to be highly useful in prediction of experimentally obtained metal concentration profiles as a function of time. Metal desorption studies indicated that Citrobacter beads could, in principle, be regenerated and reused in adsorption-desorption cycles. In an expanded scale trial, biosorbent beads were found to be useful in removal/recovery of metals such as lead from industrial wastewaters.     

Improvement of heavy metal biosorption by mycelial dead biomasses (Rhizopus arrhizus, Mucor miehei and Penicillium chrysogenum): pH control and cationic activation

Abstract: Fungal mycelial by-products from fermentation industries present a considerable affinity for soluble metal ions (e.g. Zn, Cd, Ni, Pb, Cr, Ag) and could be used in biosorption processes for purification of contaminated effluents. In this work the influence of pH on sorption parameters is characterized by measuring the isotherms of five heavy metals (Ni, Zn, Cd, Ag and Pb) with Rhizopus arrhizus biomass under pH-controlled conditions. The maximum sorption capacity for lead was observed at pH 7.0 (200 mg g^-l), while silver uptake was weakly affected. The stability of metal-biosorbent complexes is regularly enhanced by pH neutralization, except for lead. A transition in sorption mechanism was observed above pH 6.0. In addition, comparison of various industrial fungal biomasses ( R. arrhizus, Mucor miehei and Penicillium chrysogenum indicated important variations in zinc-binding and buffering properties (0.24, 0.08 and 0.05 mmol g^−l, respectively). Without control, the equilibrium pH (5.8, 3.9 and 4.0) is shown to be related to the initial calcium content of the biosorbent, pH neutralization during metal adsorption increases zinc sorption in all fungi (0.57, 0.52 and 0.33 mmol g-l) but an improvement was also obtained (0.34, 0.33 and 0.10 mmol g⁻¹) by calcium saturation of the biomass before heavy metal accumulation. Breakthrough curves of fixed bed biosorbent columns demonstrated the capacity of the biosorbent process to purify zinc and lead solutions in continuous-flow systems, and confirmed the necessity for cationic activation of the biosorbent before contact with the heavy-metal solution.     

单一与复合污染条件下两种敏感性植物对Cd、Zn、Pb的吸收效应

为了进一步研究镉、锌、铅 3种重金属元素间的相互作用以及对植物吸收重金属能力的影响 ,在模拟单一重金属污染试验研究的基础上 ,采用正交回归设计方案 ,研究了 Cd、Zn、Pb复合污染情况下紫花苜蓿和披碱草两种敏感性植物对 3种重金属的吸收效应。结果表明 ,在单一污染条件下 ,镉元素对紫花苜蓿生长的影响大于锌、铅 ,铅元素对披碱草生长的影响大于锌、镉 ;紫花苜蓿对于镉的吸收累积显著高于披碱草 ,植物内镉元素浓度最高达到 1 0 88.5 mg/kg,而披碱草对于铅元素的吸收则高于紫花苜蓿 ,植物内铅元素浓度最高达到 1 3 4 5 .5 mg/kg。在复合污染条件下 ,两种植物对铅、锌和铅、镉的吸收在不同浓度范围内分别存在存在着协同效应和拮抗效应 ;同时两种植物对锌、镉元素在实验涉及浓度范围内都存在着拮抗效应。这对于深入研究复合污染条件下重金属的土壤环境化学行为 ,对植物的综合毒性以及不同植物对重金属的吸收累积效应等 ,具有一定的参考意义     

Effects of leached alginate on metal biosorption

The Cu, Cd and Zn sorption capacity of formaldehyde-crosslinked seaweed biomass (Ascophyllum nodosum : FCAN) was studied using equilibrium methodology. The shape of sorption isotherms and biosorbent mass losses indicated that in the first uptake cycle the biosorbent leached cellular polysaccharides that formed precipitate with metal solutions influencing the sorption study and application. However, since the sorption levels of washed and non-washed biosorbents were comparable, the leached cell wall polysaccharide(s) (alginate) could not be the main component responsible for metal sorption in this case.on leave from Universidade Federal de Minas Gerais, Belo Horizonte, MG, Brazil     

Experimental and theoretical approaches for Cd(II) biosorption from aqueous solution using Oryza sativa biomass

Biomass of Oryza sativa (OS) was tested for the removal of Cd(II) ions from synthetic and real wastewater samples. Batch experiments were conducted to investigate the effects of operating parameters on Cd(II) biosorption. Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy were used to examine the surface characteristics of the Cd(II)-loaded biomass. The maximum removal efficiency of Cd(II) was 89.4% at optimum pH 6.0, biosorbent dose 10.0 g L^?1, initial Cd(II) 50 mg L^?1, and biosorbent particle size 0.5 mm. The applicability of Langmuir and Freundlich isotherms to the sorbent system implied the existence of both monolayer and heterogeneous surface conditions. Kinetic studies revealed that the adsorption process of Cd(II) followed the pseudo-second-order model (r2: 0.99). On the theoretical side, an adaptive neuro-fuzzy inference system (ANFIS) was applied to select the operating parameter that mostly influences the Cd(II) biosorption process. Results from ANFIS indicated that pH was the most influential parameter affecting Cd(II) removal efficiency, indicating that the biomass of OS was strongly pH sensitive. Finally, the biomass was confirmed to adsorb Cd(II) from real wastewater samples with removal efficiency close to 100%. However, feasibility studies of such systems on a large-scale application remain to be investigated.     

Removal of lead from aqueous solutions by Penicillium biomass

The removal of lead ions from aqueous solutions by adsorption on nonliving Penicillium chrysogenum biomass was studied. Biosorption of the Pb(+2) ion was strongly affected by pH. Within a pH range of 4 to 5, the saturated sorption uptake of Pb(+2) was 116 mg/g dry biomass, higher than that of activated charcoal and some other microorganisms. At pH 4.5, P. chrysogenum biomass exhibited selectivity for Pb(+2) over other metal ions such as Cd(+2), Cu(+2), Zn(+2), and As(+3) Sorption preference for metals decreased in the following order: Pb > Cd > Cu > Zn > As. The sorption uptake of Pb(+2) remained unchanged in the presence of Cu(+2) and As(+3), it decreased in the presence of Zn(+2), and increased in the presence of Cd(+2). (c) 1993 John Wiley & Sons, Inc.     

Characterization of Aqueous Pb(II) and Cd(II) Biosorption on Native and Chemically Modified Alstonia macrophylla Saw Dust

This study was conducted in order to understand the mechanism of Cd and Pb adsorption in aqueous solutions by raw and modified saw dust (SD) of Alstonia macrophylla. The biosorbent was characterized by Boehm titration, specific surface area, scanning electron microscopy (SEM), X-ray energy dispersion (EDAX), and Fourier transform infrared (FTIR) analyses. SD was treated using organic acids and bases. Batch studies were conducted for raw and modified SD to determine the effect of initial concentration, pH, ionic strength, and contact time on metal adsorption. The specific surface area and total basic and acidic groups of SD were 77 m²/g and 1521 and 2312 μmol/g, respectively. The adsorption of both metals onto SD was pH dependent. No ionic strength dependency was observed in adsorption of Cd and Pb at pH >6, indicating inner sphere surface complexation. Monolayer adsorption is dominant in both metal sorptions by SD. Furthermore, there is no competition between metals on adsorption and raw SD was found to be suitable for removal of Cd and Pb as compared to organic acid– or base-treated SD. Maximum adsorption capacity of SD for Cd and Pb were 30.6 and 204.2 mg/g, respectively. Results indicate that the A. macrophylla SD can be considered as a potential material for metal ion removal from wastewater.     

Uptake of cadmium ions in white-rot fungus Trametes versicolor: effect of cd (II) ions on the activity of laccase

The effects of cadmium Cd (II) ions on the physiology and biological activity of Trametes versicolor, a strain belonging to white-rotting Basidiomycetes, were examined. Cd (II) ions were added to 10-day-old cultures grown on a liquid medium, or at the time of inoculation. Our experiments showed that T. versicolor is a good cadmium biosorbent from aqueous solution, this strain removing almost all the Cd (ll) ions over the first 2h of incubation by what appears to be a rapid, energy-independent surface binding phenomenon, at the rate of approximately 2mg Cd per g mycelial dry weight. An additional slower and energy-dependent transport mechanism was also present, taking in approximately 0.3mg Cd (II) perg dry weight. It is also shown that these Cd (II) ions significantly stimulate the activity of extracellular laccase when added to 10-day-old cultures.     

Biosorption of cadmium and lead ions by ethanol treated waste baker's yeast biomass

The biosorption of cadmium and lead ions from artificial aqueous solutions using waste baker's yeast biomass was investigated. The yeast cells were treated with caustic, ethanol and heat for increasing their biosorption capacity and the highest metal uptake values (15.63 and 17.49 mg g(-1) for Cd(2+) and Pb(2+), respectively) were obtained by ethanol treated yeast cells. The effect of initial metal concentration and pH on biosorption by ethanol treated yeast was studied. The Langmuir model and Freundlich equation were applied to the experimental data and the Langmuir model was found to be in better correlation with the experimental data. The maximum metal uptake values (qmax, mg g(-1)) were found as 31.75 and 60.24 for Cd(2+) and Pb(2+), respectively. Competitive biosorption experiments were performed with Cd(2+) and Pb(2+) together with Cu(2+) and the competitive biosorption capacities of the yeast biomass for all metal ions were found to be lower than in non-competitive conditions.