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.     

Heavy metal biosorption by biomass of Ochrobactrum anthropi producing exopolysaccharide in activated sludge

The removal of chromium, cadmium and copper, toxic metals of high environmental priority due to their toxicity, from dilute aqueous solutions has been studied in the present work, applying a dead exopolysaccharide producing bacterium, Ochrobactrum anthropi, isolated from activated sludge. Particularly, the effect of pH, metal concentration and the effects of contact time were considered. Optimum adsorption pH values of chromium(VI), cadmium(II) and copper(II) were 2.0, 8.0 and 3.0 respectively. Experimental results also showed the influence of initial metal concentration on the metal uptake for dried biomass. Both the Freundlich and Langmuir adsorption models were suitable for describing the short-term biosorption of chromium(VI), cadmium(II) and copper(II) by O. anthropi.     

Heavy metal removal by novel CBD-EC20 sorbents immobilized on cellulose

Heavy metals are major contributors to pollution of the biosphere, and their efficient removal from contaminated water is required. Biosorption is an emerging technology that has been shown to be effective in removing very low levels of heavy metal from wastewater. Although peptides such as metallothioneins or phytotchelatins are known to immobilize heavy metals, peptide-based biosorbents have not been extensively investigated. In this paper, we describe the construction and expression of bifunctional fusion proteins consisting of synthetic phytochelatin (EC20) linked to a Clostridium-derived cellulose-binding domain (CBD(clos)), enabling purification and immobilization of the fusions onto different cellulose materials in essentially a single step. The immobilized sorbents were shown to be highly effective in removing cadmium at parts per million levels. Repeated removal of cadmium was demonstrated in an immobilized column. The ability to genetically engineer biosorbents with precisely defined properties could provide an attractive strategy for developing high-affinity bioadsorbents suitable for heavy metal removal.     

Mechanism of metal ion biosorption by fungal biomass

Alkali extracted mycelial biomass from Aspergillus niger, referred to as Biosorb, was found to sequester metal ions (Cd²⁺, Cu²⁺, Zn²⁺, Ni²⁺ and Co²⁺) efficiently both from dilute and concentrated solutions upto 10% of its weight (w/w). Sequestration of metal ions from a mixture was also efficient but with attendant antagonisms. The kinetics of metal binding by Biosorb indicated that it is a rapid process and about 70–80% of the metal is removed from solution in 5 min followed by a slower rate. The mechanism of metal binding is shown to be due to exchange of calcium and magnesium ions of the Biosorb during which equimolar concentrations of both the ions were released into the medium. Following this an efficient procedure for the regeneration and reuse of Biosorb was standardized by washing the biosorbent with calcium and magnesium solution (0.1 m). Biosorbents prepared from Neurospora, Fusarium and Penicillium also exhibited similar mechanisms for metal ion binding, though they had a lower metal binding capacity when compared with Biosorb. Chemical modification of carboxylic acid functional groups of the Biosorb resulted in loss of 90% of metal binding capacity which could not be restored even on regeneration. The significance of this finding on the metal sequestration mechanisms of microbial biosorbents is discussed.     

Interactive biosorption by microalgal biomass as a tool for fluoride removal

Maximum biosorption of Ca²⁺ was at 50 mg Ca²⁺ l^–1 with both Anabaena fertilissima (2.8 mg Ca²⁺ g^–1 dry wt) and Chlorococcum humicola (4.4 mg g^–1). Such Ca²⁺-treated biomasses, accumulated, respectively, 7 mg F g^–1 DW from an aqueous solution of 10 mg F l^–1 and 4.5 mg F g^–1 DW from 15 mg F l^–1. Data for both Ca²⁺ and F^– biosorption fitted the Langmuir adsorption isotherm indicating monolayer adsorption at a constant energy.     

Selective biosorption of thorium ions by an immobilized mycobacterial biomass

The biosorption of thorium and uranyl ions by cells of Mycobacterium smeamatis has been studied as a function of initial cation concentration. A similar sorption saturation level was observed for both ions. For immobilized cells, optimal conditions of metal ion retention were found for a bacterial mass/support concentration ratio of 1/6. However, selective uptake of thorium was manifest in solutions of the mixed cations. X-ray diffraction studies of the heat-dried biomasses loaded with cations showed that uranyl-loaded samples present a distinct pattern typical of ammonium uranyl phosphate, whereas thorium-loaded samples are amorphous. The microorganism used appears to have useful properties for applications in connection with separation and concentration of natural radioelements under conditions of high dilution.     

Heavy metal removal from aqueous solution by wasted biomass from a combined AS-biofilm process

This study evaluated the capability of metal biosorption by wasted biomass from a combined anaerobic-anoxic-oxic (A2O)-biofilm process with simultaneous nitrogen and phosphorus removal. Zinc, cadmium and nickel were rapidly adsorbed in 20 min by the harvested sludge from a continuous-flow pilot-plant. Biosorption equilibrium was then reached in 6h. The biosorption isotherm showed that metal biosorption behavior had fitted well to the Freundlich isotherm, but not Langmuir isotherm. The capacity constants k of Freundlich model for nickel, zinc and cadmium were 0.471, 0.298 and 0.726, respectively; the affinity constants 1/n were 0.444, 0.722 and 0.718, respectively. The order of metal affinity for the wasted biomass was Zn > Cd > Ni, which was in conformity to the other biosorption results with different biological sludge.     

Heavy metal accumulation by immobilized cells of a Citrobacter sp.

Summary Immobilized cells of a strain of a Citrobacter sp. were effective in the removal of cadmium, lead and copper from single and mixed metal flows, and from synthetic effluents. About 80% of the presented metal was removed, and this was increased to nearly 100% by the incorporation of additional immobilized cell column units.     

Modelling complexation and electrostatic attraction in heavy metal biosorption by Sargassum biomass

Biosorption, the passive accumulation of metal ions by biomass, can be used for purifying metal bearing wastewater. Seaweeds represent a readily available source of biosorbent material that possesses a high metal binding capacity. For example, Sargassum can accumulate 2 mequiv of Cd per gram of biomass i.e. 10% of its dry weight. Binding of Cd and Cu by Sargassum is an ion exchange process involving both covalent and ionic bonds. The amount of cations bound covalently or by complexation can be predicted using multi-component sorption isotherms involving 2 types of binding sites, carboxyl and sulphate. A Donnan model was used to account for the effect of ionic strength and electrostatic attraction. The use of a multi-component isotherm that included one term for Na binding was less appropriate than the Donnan model for modelling ionic strength effects. It was possible to predict metal and proton binding as a function of the pH value, metal concentration and ionic strength of the solution. This revised version was published online in June 2006 with corrections to the Cover Date.     

A batch reactor mass transfer kinetic model for immobilized biomass biosorption

Inactive cells of Rhizopus arrhizus have been immobilized into the form of particles of desirable particle size using a proprietary immobilization technique. The immobilized biomass particles are porous and are members of a new generation of biological origin adsorbents. The uranium adsorptive behavior of the biosorbent particles was modeled using a batch reactor mass transfer kinetic model of the biosorption process. The model successfully predicts the batch reactor adsorbate (uranium) concentration profiles and has provided significant insights on the way biosorbents function.     

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.     

Cadmium biosorption by Sphingomonas paucimobilis biomass

Among microorganisms isolated in Bangkok, the gram-negative bacterium Sphingomonas paucimobilis exhibited the greatest cadmium tolerance. It was able to survive in the medium containing cadmium as high as 200 mg/l. However, concentrations of cadmium at 25-200 mg/l inhibited its growth. The biosorption properties for cadmium of this bacterial biomass and the effects of environmental factors (i.e., biosorbent type, initial pH and biosorbent concentration) on the cadmium biosorption were explored. The results showed that the cadmium removal capacity of living cells was markedly higher than that of nonliving cells. Cadmium biosorption by S. paucimobilis biomass was also affected by the initial pH and biosorbent concentration.     

BTEX removal in a horizontal-flow anaerobic immobilized biomass reactor under denitrifying conditions

Because benzene, toluene, ethylbenzene, and xylenes (BTEX) and ethanol are important contaminants present in Brazilian gasoline, it is essential to develop technology that can be used in the bioremediation of gasoline-contaminated aquifers. This paper evaluates the performance of a horizontal-flow anaerobic immobilized biomass (HAIB) reactor fed with water containing gasoline constituents under denitrifying conditions. Two HAIB reactors filled with polyurethane foam matrices (5 mm cubes, 23 kg/m³ density and 95 % porosity) for biomass attachment were assayed. The reactor fed with synthetic substrate containing protein, carbohydrates, sodium bicarbonate and BTEX solution in ethanol, at an Hydraulic retention time (HRT) of 13.5 h, presented hydrocarbon removal efficiencies of 99 % at the following initial concentrations: benzene 6.7 mg/L, toluene 4.9 mg/L, m-xylene and p-xylene 7.2 mg/L, ethylbenzene 3.7 mg/L, and nitrate 60 mg N/L. The HAIB reactor fed with gasoline-contaminated water at an HRT of 20 h showed hydrocarbon removal efficiencies of 96 % at the following initial concentrations: benzene, 4.9 mg/L; toluene, 7.2 mg/L; m-xylene, 3.7 mg/L; and nitrate 400 mg N/L. Microbiological observations along the length of the HAIB reactor fed with gasoline-contaminated water confirmed that in the first segment of the reactor, denitrifying metabolism predominated, whereas from the first sampling port on, the metabolism observed was predominantly methanogenic.     

Heavy metal biosorption by fungal mycelial by-products: mechanisms and influence of pH

Summary Mycelial wastes of Rhizopus arrhizus, used in fermentation industries to produce lipases, were studied for their ability to absorb various heavy metal ions (Ni, Zn, Cd and Pb). Chelation of all these ions occurs by a chemical, equilibrated and saturatable mechanism, following the Langmuir adsorption model. Data transformation allowed us to calculate maximum uptake and dissociation constants of the sorption reaction. We also investigated the influence of pH on metal accumulation. Sorption capacity variations between different biosorbent types (Rhizopus, Mucor, Penicillium, and Aspergillus), could be related to their acidity. pH neutralisation during the sorption reaction considerably enhanced zinc chelation (up to 56 mg/g). Previous NaOH treatment of mycelial wastes also increased their capacity for metal sorption. We report R. arrhizus metal uptake curves versus pH, using a pH-stat system. Optimal adsorption was achieved at neutral pH for nickel and zinc, pH 5.0 for lead, and inhibition of chelation was observed when the pH decreased. These results illustrate the importance of pH during the adsorption process, indicating a competitive mechanism for chelation between heavy metal ions and protons at cell wall adsorption sites. Correspondence to: J.-C. Roux     

Continuous biosorption of cadmium by Moringa olefera in a packed column

The biosorption of Cd(II) by Moringa oleifera using a batch system and a continuous up flow mode in a fixed bed column was studied. Batch adsorption experiments were performed as a function of pH, biosorbent dose, contact time, volume of the solution, and initial metal concentration. The adsorption isotherms obtained fitted well into the Freundlich and Langmuir isotherms. The dynamic removal of cadmium by powdered seed of the Moringa oleifera was studied in a packed column. The effect of bed height (4 and 8 cm) and flow rate (2 and 5mL/min) on biosorption process was investigated and the experimental breakthrough curves were obtained. Results showed that by increasing the bed height and decreasing the flow rate, the breakthrough and exhaustion times increased. The break-through time was considered as a measure of the column performance. The maximum break-through time of 320 min was achieved at the operating condition of 2 mL/min influent flow rate and bed height of 8 cm.     

Cadmium biosorption by Streptomyces pimprina waste biomass

Biosorption of cadmium from solution was studied using a hamycin-producing Streptomyces pimprina waste biomass. Mycelial pretreatments with 80% ethanol increased the uptake of cadmium threefold. The rate of uptake of the metal was maximum in the first 10 min and the equilibration of the system was achieved after 60 min. At pH 2.0 there was no adsorption of cadmium; however, as the pH of the solution increased, a rise in the adsorption could be noticed, which peaked at pH 5.0. The uptake of cadmium was found to increase linearly as a function of cadmium concentration up to 500 mg/l. The data could be fitted to Freundlich and Langmuir models for absorption processes. A 0.1 M EDTA solution could desorb cadmium loaded on S. pimprina biomass with the highest efficiency.     

Optimization of flow rate,initial metal ion concentration and biomass density for maximum removal of Cu2+ by immobilized Microcystis

The potential of alginate-immobilized Microcystis packed in a column for maximum removal of Cu²⁺ at different flow rates, biomass, and initial metal ion concentration was assessed in a continuous flow system. Although Cu²⁺ removal did occur at all the flow rates tested, it was maximum (54%) at 0.75-ml min⁻¹ flow rate, 30 μg ml⁻¹ initial metal ion concentration and 0.016 g biomass. Cu²⁺ removal was influenced by inlet metal ion concentration and biomass density. An increase in the biomass concentration from 0.016 to 0.128 g resulted in an apparent increase in percentage removal but the Cu²⁺ adsorbed per unit dry wt. declined. When the flow rate (0.75 ml min⁻¹) and biomass density (0.064 g) were kept constant and the inlet metal ion concentration was varied from 10 to 150 μg ml⁻¹, a 68% removal of Cu²⁺ was obtained at 50 μg ml⁻¹ initial concentration in a time duration of 15 min. The metal-laden columns were efficiently desorbed and regenerated following elution with double distilled water (DDW) (pH 2) (89%). This was followed by 1 mm EDTA > 1 mm NTA > 0.1 mm EDTA > 1 mm HCl > 1 mm HNO₃ > 5 mm CaCl₂ > DDW (pH 7.0) > 1 mm NaHCO₃ > 1 mm CaCl₂. Of the total (2.83 mg) adsorbed Cu²⁺, 1.89 mg (67%) was desorbed by DDW (pH 2) within the first 20 min of elution time. Thereafter the desorption rate slowed down and only 22% (0.632 mg) desorption was obtained in the last 20 min. In contrast to water pH 2, the desorption of Cu²⁺ by 1 mm EDTA was very slow, the maximum being 8% after 40 min of elution. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mechanism of Biosorption of Heavy Metals by Mucor rouxii

Fungi such as Aspergillus niger and Mucor rouxii are capable of removing heavy metals from aqueous solutions. The role various functional groups play in the cell wall of M. rouxii in metal biosorption of lead, cadmium, nickel and zinc was investigated in this paper. The biomass was chemically treated to modify the functional carboxyl, amino and phosphate groups. These modifications were examined by means of infrared spectroscopy. It was found that an esterification of the carboxyl groups and phosphate and a methylation of the amine groups significantly decreased the biosorption of the heavy metals studied. Thus, the carboxylate, amine and phosphate groups were recognized as important in the biosorption of metal ions by M. rouxii biomass. The role the lipids fraction play was not significant. The study showed that Na, K, Ca and Mg ions were released from the biomass after biosorption of Pb, Cd, Ni and Zn, indicating that ion exchange was a key mechanism in the biosorption of metal ions by M. rouxii biomass.     

Heavy metal removal from a multi-metal solution and wastewater by Salvinia natans

Salvinia showed capacity to accumulate and hence remove more than one heavy metal from multi-metal solutions, though efficiency for heavy metal uptake varied for each metal present in different combinations. The pattern of heavy metal accumulation was confirmed by energy-dispersive X-ray fluorescence (EDXRF) analysis. There was a gradual decrease in heavy metal content in the wastewater samples when fresh biomass was replenished at definite time intervals of treatment. Zn, Cu, Ni and Cr removal to the extent of 84.8%, 73.8%, 56.8%, and 41.4%, respectively, was noted after four samplings of fresh biomass replenishment. Salvinia therefore can be recommended as a species for cleaning water contaminated with heavy metals.     

Ethanol and toluene removal in a horizontal-flow anaerobic immobilized biomass reactor in the presence of sulfate

In this study it is reported the operation of a horizontal-flow anaerobic immobilized biomass (HAIB) reactor under sulfate-reducing condition which was also exposed to different amounts of ethanol and toluene. The system was inoculated with sludge taken from up-flow anaerobic sludge blanket (UASB) reactors treating refuses from a poultry slaughterhouse. The HAIB reactor comprised of an immobilized biomass on polyurethane foam and ferrous and sodium sulfate solutions were used (91 and 550 mg/L, respectively), to promote a sulfate-reducing environment. Toluene was added at an initial concentration of 2.0 mg/L followed by an increased range of different amendments (5, 7, and 9 mg/L). Ethanol was added at an initial concentration of 170 mg/L followed by an increased range of 960 mg/L. The reactor was operated at 30(+/-2) degrees C with hydraulic detention time of 12 h. Organic matter removal efficiency was close to 90% with a maximum toluene degradation rate of 0.06 mg(toluene)/mg(vss)/d. Sulfate reduction was close to 99.9% for all-nutritional amendments. Biofilm microscopic characterization revealed a diversity of microbial morphologies and DGGE-profiling showed a variation of bacterial and sulfate reducing bacteria (SRB) populations, which were significantly associated with toluene amendments. Diversity of archaea remained unaltered during the different phases of this experiment. Thus, this study demonstrates that compact units of HAIB reactors, under sulfate reducing conditions, are a potential alternative for in situ aromatics bioremediation.