Engineered Biofilms for Metal Ion Removal

Firstly, biofilm and biosorbents are defined. Mechanisms of interactions between metal ions and biofilm are discussed in terms of diffusion, mass transfer and sorption. In a second step, different processes using biofilm to remove heavy metal in aqueous solutions are presented. The continuously stirred processes are described for metal ion removal in wastewater by biofilm coating particles. In this case, the equilibrium data obtained with isotherm curves show a good adsorption of several metal ions onto biofilm. Examples of adsorption capacities for a large number of microorganisms and heavy metal ions are presented. The fixed bed reactors packed with grains coated with a biofilm are efficient to get a sorption (adsorption or ion exchange) of cations. The pressure drop is calculated with classical equations. Some values such as adsorption capacities and breakthrough times are got from the breakthrough curves. Several models (Adams-Bohart, mass transfer, and homogeneous surface diffusion models) are applied to get design data. A new approach using neural network to model breakthrough curves is proposed and discussed.     

Engineering of microorganisms towards recovery of rare metal ions

The bioadsorption of metal ions using microorganisms is an attractive technology for the recovery of rare metal ions as well as removal of toxic heavy metal ions from aqueous solution. In initial attempts, microorganisms with the ability to accumulate metal ions were isolated from nature and intracellular accumulation was enhanced by the overproduction of metal-binding proteins in the cytoplasm. As an alternative, the cell surface design of microorganisms by cell surface engineering is an emerging strategy for bioadsorption and recovery of metal ions. Cell surface engineering was firstly applied to the construction of a bioadsorbent to adsorb heavy metal ions for bioremediation. Cell surface adsorption of metal ions is rapid and reversible. Therefore, adsorbed metal ions can be easily recovered without cell breakage, and the bioadsorbent can be reused or regenerated. These advantages are suitable for the recovery of rare metal ions. Actually, the cell surface display of a molybdate-binding protein on yeast led to the enhanced adsorption of molybdate, one of the rare metal ions. An additional advantage is that the cell surface display system allows high-throughput screening of protein/peptide libraries owing to the direct evaluation of the displayed protein/peptide without purification and concentration. Therefore, the creation of novel metal-binding protein/peptide and engineering of microorganisms towards the recovery of rare metal ions could be simultaneously achieved.     

A novel screening method for microorganisms that efficiently remove heavy metals from aqueous solution

A novel bioassay system for estimating concentrations of several heavy metal ions was carried out with yeast mutants which are highly sensitive to heavy metal ions. The method does not need an atomic adsorption spectrometer or other special equipment. It is suitable for screening of microorganisms that efficiently remove heavy metal ions from aqueous solution.     

Removal of selected metal ions from aqueous solution using modified corncobs

The objective of this study was to convert corncobs to metal ion adsorbents for wastewater treatment. Ground corncobs were modified with either 0.6 M citric acid (CA) or 1.0 M phosphoric acid (PA) to help improve their natural adsorption capacity. The effect of a combination of wash and modification treatment was tested for corncob adsorption efficiency with five different metal ions (cadmium, copper, lead, nickel, zinc) individually or in a mixed solution containing each metal at a 20 mM concentration. Results were compared to those of commercial resins Amberlite IRC-718, Amberlite 200, Duolite GT-73 and carboxymethylcellulose (CMC). Modified corncobs showed the same adsorption efficiency as Duolite GT-73 for cadmium, copper, nickel and zinc ions and had greater adsorption than CMC for nickel and zinc ions. For mixed metals, the modified corncobs exhibited the same adsorption efficiency as Duolite GT-73 for cadmium and copper ions and the same or higher adsorption than Amberlite IRC-718 for lead ions. Adsorption capacities of modified samples were compared to those of Amberlite IRC-718, Amberlite 200 and Duolite GT-73. Commercial resins generally had higher adsorption capacities than modified corncobs. However, the adsorption capacity of modified corncobs for copper and lead ions was equivalent to Duolite GT-73, but was lower than for Amberlite IRC-718 or Amberlite 200. Depending on the specific metal ion and the presence or absence of other metal ions, chemically modified corncobs were at least equivalent in adsorption properties to all of the commercial cation exchange resins examined in this study.     

Selective adsorption and recovery of precious metal ions using protein-rich biomass as efficient adsorbents

Various types of protein-rich biomass were examined as selective and environment-friendly adsorbents for precious metal ions. In the presence of base metal ions, Au³⁺, Pd²⁺ and Pt⁴⁺ ions were selectively adsorbed to samples of protein-rich biomass. Among the biomass samples tested, egg-shell membrane exhibited the highest adsorption ability and had high selectivity for Au, Pd and Pt ions. The maximum adsorption amount of Au, Pd and Pt ions to egg-shell membrane was approximately 250, 110 and 50 mg/g, respectively, in the presence of 0.1 M HCl. Microscopic observations and metal-ion desorption studies suggested that the precious metal ions were adsorbed and a portion of them was reduced to form metal nanoparticles on the egg-shell membrane, leading to high adsorption ratios. Investigations using glycoproteins indicated the importance of sugar chains in the adsorption of Au ions to the egg-shell membrane. Successful recovery of Au, Pd and Pt ions from industrial waste solutions was also demonstrated using egg-shell membrane. Biomass sheets (1 mm thick) made from egg-shell membrane also exhibited adsorption abilities for precious metal ions.     

Activated carbon prepared from biomass as adsorbent: elimination of Ni(II) from aqueous solution.

Activated carbon (AC) prepared from waste Parthenium was used to eliminate Ni(lI) from aqueous solution by adsorption. Batch mode adsorption experiments are carried out, by varying contact time, metal ion concentration, carbon concentration, pH and desorption to assess kinetic and equilibrium parameters. They allowed initial adsorption coefficient, adsorption rate constant and maximum adsorption capacities to be computed. The adsorption data were modeled by using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacity (Q0) calculated from the Langmuir isotherm was 54.35 mg Ni(II)/g of AC at initial pH of 5.0 and 20 degrees C, for the particle size 250-500 microm. Increase in pH from 2 to 10 increased percent removal of metal ion. The regeneration by HCl of Ni(II)-saturated carbon by HCl, allowed suggestion of an adsorption mechanism by ion-exchange between metal ion and H+ ions on the AC surfaces. Quantitative recovery of Ni(II) was possible with HCl.     

Adsorption of Cu(II) and Pb(II) onto diethylenetriamine-bacterial cellulose

Diethylenetriamine-bacterial cellulose (EABC) was synthesized by amination with diethylenetriamine on bacterial cellulose (BC). Its adsorption properties for Cu(II) and Pb(II) were investigated. The parameters affecting the metal ions adsorption, such as contact time, solution pH, and initial metal ions concentration have been investigated. The adsorption kinetics and adsorption isotherms were further studied. The results show that the adsorption rate could be well fitted by pseudo-second-order rate model, and adsorption isotherm could be described by the Langmuir model. The regeneration of EABC was also studied. This study provides the relatively comprehensive data for the EABC application to the removal of metal ion in the wastewater.     

Adsorption of heavy metals from electroplating wastewater by wood sawdust

Poplar wood sawdust was examined for adsorption as a replacement for current, more expensive methods of removing copper, zinc and cadmium from electroplating wastewater. Langmuir, Freundlich, BET and competitive Langmuir (two competing ions) isotherms were fitted to experimental data and the goodness of their fit for adsorption was compared. The shapes of isotherms obtained fitted well with multilayer adsorption. This was established and confirmed through solid correspondence between the BET equation and experimental data, in contrast to an observed monolayer adsorption of metal ions on poplar sawdust in single metal-water solutions. The adsorption of copper ions from a mixture (in wastewater) was better than that from a single metal solution. The adsorptions of zinc ions from wastewater and from model water were approximately equal, while that of cadmium ions was significantly lower from the wastewater than from model water. The aforementioned suggests that the presence of other ions in wastewater hindered adsorption of cadmium ions.     

Removal of cadmium from aqueous solution by Nordmann fir (Abies nordmanniana (Stev.) Spach. Subsp. nordmanniana) leaves

The utility of Nordmann fir (Abies nordmanniana (Stev.) Spach. Subsp. nordmanniana) leaves from Eastern Black Sea region for the removal (sorption) of metal ions from aqueous solutions was investigated. For this, the optimum values of pH, time, metal concentration, leaf concentration, leaf particle size and adsorption capacity were determined. Also the recovery conditions of the metals from leaves were studied. Cd metal was selected because of its toxic properties. Freundlich isotherm model was used to describe the adsorption behaviour and the experimental results obtained for Cd(2+) adsorption, followed this model well. The utility of Nordmann fir leaves to remove toxic metals from aqueous solutions was proved. Hence, this study showed that the leaves of Nordmann fir can provide cheap source as biosorbents for toxic metal removal from natural or wastewaters.     

The use ofZoogloea ramigera in waste water treatment containing Cr(VI) and Cd(II) ions

Summary Optimum fermentation conditions forZ. ramigera were determined and various parameters which affected adsorption rates of chromium and cadmium ions onZ. ramigera were investigated. At 25°C the optimum adsorption pH of Cr(VI) and Cd(II) ions were 2.0 and 6.0 respectively. The adsorption rate of chromium and cadmium ion increased by increasing initial metal ion concentration up to 75 and 50 ppm respectively: at higher initial metal ion concentrations, the adsorption rates decreased.     

Effective display of metallothionein tandem repeats on the bioadsorption of cadmium ion

To increase the level of adsorption of heavy metal ions in surface-engineered yeasts, a yeast metallothionein (YMT) was tandemly fused and displayed by means of an α-agglutinin-based display system. The display of the YMT and its tandem repeats was examined by immunofluorescent labeling. The adsorption and recovery of Cd²⁺ on the cell surface was increasingly enhanced with increasing number of tandem repeats. All Cd²⁺-binding sites in the YMT tandem repeats were suggested to be completely occupied. To investigate the relationship between cell-surface adsorption and protection against heavy metal ion toxicity, the tolerance of these surface-engineered yeasts to Cd²⁺ was examined by growing in Cd²⁺-containing liquid medium. The rate of growth was found to be dependent on the number of displayed tandem repeats of YMT. These results suggest that the characteristics of surface-engineered yeasts as a bioadsorbent were dependent on the ability of the displayed proteins to bind metal ions, and the adsorption of heavy metal ions on the cell surface plays a major role in the ability of the cells to resist the toxic effects of metal ions.     

Molecular design of the microbial cell surface toward the recovery of metal ions

The genetic engineering of microorganisms to adsorb metal ions is an attractive method to facilitate the environmental cleanup of metal pollution and to enrich the recovery of metal ions such as rare metal ions. For the recovery of metal ions by microorganisms, cell surface design is an effective strategy for the molecular breeding of bioadsorbents as an alternative to intracellular accumulation. The cell surface display of known metal-binding proteins/peptides and the molecular design of novel metal-binding proteins/peptides have been performed using a cell surface engineering approach. The adsorption of specific metal ions is the important challenge for the practical recovery of metal ions. In this paper, we discuss the recent progress in surface-engineered bioadsorbents for the recovery of metal ions.     

趋磁细菌培养及用于吸附分离贵重金属离子

生物吸附是有效处理含较低浓度重金属离子废水的廉价方法之一。本文通过对污水处理厂活性污泥的富集和培养, 经过分离、纯化活性污泥中的细菌, 最终得到了趋磁细菌MTB-11s。通过16S rDNA鉴定, 菌株MTB-11s属于代尔夫特菌属。对趋磁细菌的生物吸附性能进行了研究, 实验结果表明, 趋磁细菌MTB-11s对不同金属离子具有选择吸附特性, 其对银离子的吸附表现为快速过程, 温度对其吸附性能的影响较小, pH值为4?8时吸附率较高; 随着干菌浓度的增加, 吸附率不断升高, 最终趋于平稳; 随着银离子初始浓度的增加, 吸附率呈现先升高后降低的趋势。在菌量充足或金属离子浓度较低时, 铜、钴离子的存在能促进银离子的吸附, 其他范围则表现为竞争吸附。     

Ternary biosorption studies of Cd(II), Cr(III) and Ni(II) on shelled Moringa oleifera seeds

Competitive biosorption of Cd(II), Cr(III) and Ni(II) on unmodified shelled Moringa oleifera seeds (SMOS) present in ternary mixture were compared with the single metal solution. The extent of adsorption capacity of the ternary metal ions tested on unmodified SMOS was low (10-20%) as compared to single metal ions. SMOS removed the target metal ions in the selectivity order of Cd(II) > Cr(III) > Ni(II). Sorption equilibria, calculated from adsorption data, explained favorable performance of biosorption system. Regeneration of exhausted biomass was also attempted for several cycles with a view to restore the sorbent to its original state.     

Cooperative adsorption of critical metal ions using archaeal poly-γ-glutamate

Antimony, beryllium, chromium, cobalt (Co), gallium (Ga), germanium, indium (In), lithium, niobium, tantalum, the platinoids, the rare-earth elements (including dysprosium, Dy), and tungsten are generally regarded to be critical (rare) metals, and the ions of some of these metals are stabilized in acidic solutions. We examined the adsorption capacities of three water-soluble functional polymers, namely archaeal poly-γ-glutamate (L-PGA), polyacrylate (PAC), and polyvinyl alcohol (PVA), for six valuable metal ions (Co²⁺, Ni²⁺, Mn²⁺, Ga³⁺, In³⁺, and Dy³⁺). All three polymers showed apparently little or no capacity for divalent cations, whereas L-PGA and PAC showed the potential to adsorb trivalent cations, implying the beneficial valence-dependent selectivity of anionic polyelectrolytes with multiple carboxylates for metal ions. PVA did not adsorb metal ions, indicating that the crucial role played by carboxyl groups in the adsorption of crucial metal ions cannot be replaced by hydroxyl groups under the conditions. In addition, equilibrium studies using the non-ideal competitive adsorption model indicated that the potential for L-PGA to be used for the removal (or collection) of water-soluble critical metal ions (e.g., Ga³⁺, In³⁺, and Dy³⁺) was far superior to that of any other industrially-versatile PAC materials.     

Olive oil waste as a biosorbent for heavy metals

The sourcing of novel, inexpensive biowastes such as olive mill waste (OMW) from the two-decanter olive-oil-production system offers potential for the removal of metal ions by biosorption. OMW can be used in repeated regeneration cycles for the adsorption of heavy metals from aqueous solutions. The metal ions sequestered can be released in an acid solution until the concentration of these metal ions reaches a level where conventional methods can be used to provide economic metal recovery and potential revenue generation. The ability of this biomass to adsorb more than one metal ion from solution may increase its potential for application in the wastewater industry since the majority of industrial effluents contain more than one metallic species. Metal ion adsorption was found to increase with the speed of agitation and at an optimum pH value of between 4 and 7.     

Kinetic modeling and equilibrium studies during cadmium biosorption by dead Sargassum sp. biomass

A basic investigation on the removal of cadmium(II) ions from aqueous solutions by dead Sargassum sp. was conducted in batch conditions. The influence of different experimental parameters; initial pH, shaking rate, sorption time, temperature and initial concentrations of cadmium ions on cadmium uptake was evaluated. Results indicated that cadmium uptake could be described by the Langmuir adsorption model, being the monolayer capacity negatively affected with an increase in temperature. Analogously, the adsorption equilibrium constant decreased with increasing temperature. The kinetics of the adsorption process followed a second-order adsorption, with characteristic constants increasing with increasing temperature. Activation energy of biosorption could be calculated as equal to 10 kcal/mol. The biomass used proved to be suitable for removal of cadmium from dilute solutions. Its maximum uptake capacity was 120 mg/g. It can be considered an optimal result when compared to conventional adsorbing materials. Thus Sargassum sp. has great potential for removing cadmium ions especially when concentration of this metal is low in samples such as wastewater streams.     

Uptake of cadmium and zinc by the alga Chlorella vulgaris: II. Multi-ion situation

Many microorganisms are capable of sequestering and concentrating heavy metals from their aqueous environment. While much research has beep carried out on the uptake of single species of metal ions, little attention seems to have been given to the study of multimetal ion systems. A mathematical model has previously been developed to describe the uptake of individual metal species by a microorganism. The model proposes two sequential processes: an initial rapid uptake due to cellular surface adsorption and a subsequent slow uptake due to membrane transport of the metal into the cells. This article extends the treatment by considering the uptake of two metal species together, cadmium and zinc, under different experimental conditions. The results are discussed in terms of possible mechanistic interactions.     

Cell surface-engineered yeast displaying a histidine oligopeptide (hexa-His) has enhanced adsorption of and tolerance to heavy metal ions

A histidine oligopeptide (hexa-His) with the ability to chelate divalent heavy metal ions was displayed on the yeast cell surface for the purpose of enhanced adsorption of heavy metal ions. We genetically fused a hexa-His-encoding gene with the gene encoding the C-terminal half of alpha-agglutinin that includes a glycosylphosphatidylinositol anchor attachment signal sequence and attached the hexa-His peptide on the cell wall of Saccharomyces cerevisiae. This surface-engineered yeast adsorbed three to eight times more copper ions than the parent strain and was more resistant to copper (4 mM) than the parent (below 1 mM at pH 7.8). It was possible to recover about a half of the copper ions adsorbed by whole cells with EDTA treatment without disintegrating the cells. Thus, we succeeded in constructing a novel yeast cell with both tolerance to toxic contaminants and enhanced adsorption of metal ions onto the cell surface.     

Chemical factors influencing adsorption of bacteriophage MS2 to membrane filters.

Antichaotropic salts, such as magnesium sulfate, and metal chelators, such as citrate ions, promoted adsorption of bacteriophage MS2 to membrane filters. In contrast, compounds that disrupt hydrophobic interactions, such as chaotropic salts, urea, Tween 80, and ethanol, did not promote adsorption of MS2 to membrane filters and counteracted the ability of magnesium sulfate to promote such adsorption. These results provide evidence that magnesium sulfate promotes the association of MS2 with membrane filters primarily by strengthening hydrophobic interactions between the virus and the filters.