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     

Wechselwirkungen zwischen Mikroorganismen und Metallionen

Microorganisms are able to interact with metal ions in aqueous solutions and to accumulate considerable amounts of them. The mechanism of the accumulation depends on the physiological state of the cells. In the case of resting cells the binding reaction takes place on the surface of the cell wall as a sorption process. The kinetic of the sorption processes in dependence of the physiological state of the cells, the concentration of Hg²⁺ and Cd²⁺-ions on the solution and the pH and temperature has been investigated. Beyond that possibilities for the desorption of the metals from the biomass have been tested.     

Silver Sorption to Myxococcus xanthus Biomass

This paper deals with silver sorption to Myxococcus xanthus biomass. The dry biomass of this microorganism is shown to be a good sorbent for the recovery of silver present at low solution concentrations. Between initial silver concentrations of 2 and 0.05 mM, the percentage of accumulation ranges from 8.12% to 75% of the total silver present in the solution. Transmission electron microscopy study of M. xanthus wet biomass after silver accumulation shows the sorption within the extracellular polysaccharide, on the cell wall, and in the cytoplasm. The presence of silver deposits in the cytoplasm indicates that at least two mechanisms are involved in silver sorption by this bacterium biomass. First, silver was bound to the cell surface and extracellular polysaccharide, and second, a silver intracellular deposition process took place. The higher amount of silver deposits in the extracellular polysaccharide, present abundantly in M. xanthus cells, explains the capacity of this bacterium to bind silver efficiently. The results obtained indicate that the removal of silver by M. xanthus from the diluted solutions could be used in recycling this valuable metal. One interesting observation of this investigation is the crystalline form, possibly as chlorargyrite, in which the silver deposits are found in the M. xanthus cells.     

Desorption of cobalt-laden algal biosorbent

Following an effective accumulation of cobalt by nonliving algal biomass of Ascophyllum nodosum, the desorption release of the metal from the biosorbent was examined using H(2)SO(4), HCl, NH(4)OH, KHCO(3), EDTA, KSCN, KCl, and CaCl(2) solutions. The solution of CaCl(2) (0.05M) in HCl appeared to be the best eluant capable of desorbing more than 96% of the sequestered cobalt at the optimum pH 2-3. The optimum solid-to-liquid ratio was more than 10 with the cobalt reuptake capacity of the biosorbent undiminished. The effect of temperature on the elution process and the elution rate was not significant up to 60 degrees C. The infrared (IR) spectra of the native and the eluted biomass did not show significant differences. The electron micrographs of the algal biomass taken after washing it with the CaCl(2) (0.1M) eluant solution indicated no damage to the cells and cell walls, while strong acid, alkaline, and KSCN treatment resulted in some changes in the cellular structure. The kinetics of the cobalt stripping process was quite rapid. The required contact time for the complete metal removal from the biomass was shorter than 2 h, even for the highest levels of cobalt initially deposited on the biomass.     

Use of algae for removing heavy metal ions from wastewater: progress and prospects

Many algae have immense capability to sorb metals, and there is considerable potential for using them to treat wastewaters. Metal sorption involves binding on the cell surface and to intracellular ligands. The adsorbed metal is several times greater than intracellular metal. Carboxyl group is most important for metal binding. Concentration of metal and biomass in solution, pH, temperature, cations, anions and metabolic stage of the organism affect metal sorption. Algae can effectively remove metals from multi-metal solutions. Dead cells sorb more metal than live cells. Various pretreatments enhance metal sorption capacity of algae. CaCl2 pretreatment is the most suitable and economic method for activation of algal biomass. Algal periphyton has great potential for removing metals from wastewaters. An immobilized or granulated biomass-filled column can be used for several sorption/desorption cycles with unaltered or slightly decreased metal removal. Langmuir and Freundlich models, commonly used for fitting sorption data, cannot precisely describe metal sorption since they ignore the effect of pH, biomass concentration, etc. For commercial application of algal technology for metal removal from wastewaters, emphasis should be given to: (i) selection of strains with high metal sorption capacity, (ii) adequate understanding of sorption mechanisms, (iii) development of low-cost methods for cell immobilization, (iv) development of better models for predicting metal sorption, (v) genetic manipulation of algae for increased number of surface groups or over expression of metal binding proteins, and (vi) economic feasibility.     

Use of Algae for Removing Heavy Metal Ions From Wastewater: Progress and Prospects

ABSTRACT

Many algae have immense capability to sorb metals, and there is considerable potential for using them to treat wastewaters. Metal sorption involves binding on the cell surface and to intracellular ligands. The adsorbed metal is several times greater than intracellular metal. Carboxyl group is most important for metal binding. Concentration of metal and biomass in solution, pH, temperature, cations, anions and metabolic stage of the organism affect metal sorption. Algae can effectively remove metals from multi-metal solutions. Dead cells sorb more metal than live cells. Various pretreatments enhance metal sorption capacity of algae. CaCl₂ pretreatment is the most suitable and economic method for activation of algal biomass. Algal periphyton has great potential for removing metals from wastewaters. An immobilized or granulated biomass-filled column can be used for several sorption/desorption cycles with unaltered or slightly decreased metal removal. Langmuir and Freundlich models, commonly used for fitting sorption data, cannot precisely describe metal sorption since they ignore the effect of pH, biomass concentration, etc. For commercial application of algal technology for metal removal from wastewaters, emphasis should be given to: (i) selection of strains with high metal sorption capacity, (ii) adequate understanding of sorption mechanisms, (iii) development of low-cost methods for cell immobilization, (iv) development of better models for predicting metal sorption, (v) genetic manipulation of algae for increased number of surface groups or over expression of metal binding proteins, and (vi) economic feasibility.     

Biosorption of cadmium by biomass of marine algae

Biomass of nonliving, dried brown marine algae Sargassum natans, Fucus vesiculosus, and Ascophyllum nodosum demonstrated high equilibrium uptake of cadmium from aqueous solutions. The metal uptake of cadmium from aqueous solutions. The metal uptake by these materials was quantitatively evaluated using sorption isotherms. Biomass of A. nodosum accumulated the highest amount of cadmium exceeding 100 mg Cd(2+)/g (at the residual concentration of 100 mg Cd/L and pH 3.5), outperforming a commercial ion exchange resin DUOLITE GT-73. A new biosorbent material based on A. nodosum biomass was obtained by reinforcing the algal biomass by formaldehyde cross-linking. The prepared sorbent possessed good mechanical properties, chemical stability of the cell wall polysaccharides and low swelling volume. Desorption of deposited cadmium with 0.1-0.5M HCI resulted in no changes of the biosorbent metal uptake capacity through five subsequent adsorption/desorption cycles. There was no damage to the biosorbent which retained its macroscopic appearance and performance in repeated metal uptake/elution cycles. (c) 1993 Wiley & Sons, Inc.     

Biosorption of Pb2+ from aqueous solution by waste biomass of aerial roots of Rhizophora mangle (red mangrove)

The processing waste of the aerial roots of Rhizophora mangle was used in both its unmodified or mercaptoacetic acid (MAA) modified form for the sorption of Pb2+ from aqueous solution. The biomass rapidly and strongly sorbed Pb2+ at pH 5.0, which indicated chemisorption. A significant increase in Pb2+ sorption resulted from MAA treatment of the biomass, indicating that sorption occurs through an ion-exchange process. From sorption-capacity experiments, the unmodified and modified materials extracted, at pH 5, 31.3 and 85.5 mg of Pb2+ per gram of biomass, respectively, from aqueous solutions. Our studies may contribute to an innovative method for the economical and ecologically save removal and recovery of heavy-atom metal ions from contaminated waters through biosorption.     

Metals sorption from aqueous solutions by Kluyveromyces marxianus: Process optimization,equilibrium modeling and chemical characterization

The dead Kluyveromyces marxianus biomass, a fermentation industry waste, was used to explore its sorption potential for lead, mercury, arsenic, cobalt, and cadmium as a function of pH, biosorbent dosage, contact time, agitation speed, and initial metal concentration. The equilibrium data fitted the Langmuir model better for cobalt and cadmium, but Freundlich isotherm for all metals tested. At equilibrium, the maximum uptake capacity (Qmax) was highest for lead followed by mercury, arsenic, cobalt, and cadmium. The RL values ranged between 0–1, indicating favorable sorption of all test metals by the biosorbent. The maximum Kf value of Pb showed its efficient removal from the solution. However, multi-metal analysis depicted that sorption of all metals decreased except Pb. The potentiometric titration of biosorbent revealed the presence of functional groups viz. amines, carboxylic acids, phosphates, and sulfhydryl group involved in heavy metal sorption. The extent of contribution of functional groups and lipids to biosorption was in the order: carboxylic>lipids>amines>phosphates. Blocking of sulfhydryl group did not have any significant effect on metal sorption.     

Biosorption of binary mixtures of copper and cobalt by Penicillium brevicompactum

This work reports on a study of the biosorption of copper and cobalt, both singly and in combination (in equimolar concentrations), by the resting cells of Penicillium brevicompactum. Equilibrium batch sorption studies were carried out at 30 degrees C and pH 5.0 for a contact time of 1 hour to guarantee that equilibrium was reached. The equilibrium data were analyzed using the Langmuir and Freundlich isotherms. The adsorption of binary mixtures of heavy metal solutions on the fungal biomass was found to be of competitive type where the adsorption capacity for any single metal decreased in the presence of the other. The cobalt ions showed a higher affinity for Penicillium brevicompactum than the copper ions.     

Cobalt sorption onto anaerobic granular sludge: isotherm and spatial localization analysis

This study investigated the effect of different feeding regimes on the cobalt sorption capacity of anaerobic granular sludge from a full-scale bioreactor treating paper mill wastewater. Adsorption experiments were done with non-fed granules in monometal (only Co) and competitive conditions (Co and Ni in equimolar concentrations). In order to modify the extracellular polymeric substances and sulfides content of the granules, the sludge was fed for 30 days with glucose (pH 7, 30 degrees C, organic loading rate=1.2 g glucose l(-1) day-1) in the presence (COD/SO4(2-)=1) or absence of sulfate. The partitioning of the sorbed cobalt between the exchangeable, carbonates, organic matter/sulfides and residual fractions was determined using a sequential extraction procedure (modified Tessier). Experimental equilibrium sorption data for cobalt were analysed by the Langmuir, Freundlich and Redlich-Peterson isotherm equations. The total Langmuir maximal sorption capacity of the sludge fed with glucose and sulfate loaded with cobalt alone displayed a significantly higher maximal cobalt sorption (Qmax =18.76 mg g-1 TSS) than the sludge fed with glucose alone (Qmax =13.21 mg g-1 TSS), essentially due to an increased sorption capacity of the exchangeable (30-107%) and organic/sulfides fractions (70-30%). Environmental scanning electron microscopy coupled with an energy dispersive X-ray analysis of granular cross-sections showed that mainly iron minerals (i.e. iron sulfides) were involved in the cobalt accumulation. Moreover, the sorbed cobalt was mainly located at the edge of the granules. The sorption characteristics of the exchangeable and carbonates fractions fitted well to the Redlich-Peterson model (intermediate multi-layer sorption behaviour), whereas the sorption characteristics of the organic matter/sulfides and residual fractions fitted well to the Langmuir model (monolayer sorption behaviour). The organic matter/sulfides fraction displayed the highest affinity for cobalt for the three sludge types investigated.     

Sorption of lead, cadmium, and zinc on sulfur-containing chemically modified wastes of fluted pumpkin (Telfairia occidentalis Hook f.)

We have tested the applicability of regular as well as sulfanylacetic acid (SA) modified fluted pumpkin waste biomass as adsorbents for Pb2+, Cd2+, and Zn2+ aqueous solutions by means of the batch-sorption technique. The data revealed that SA modification produces a larger surface area, enhancing the metal-ion binding capacity of the biomass. The sorption process was examined by means of Freundlich and Langmuir models. The kinetic study showed that the sorption rates can be described by a pseudo-second-order process. The rate constants for the control biomass (CB) were 2.2x10(-2), 4.4x10(-2), and 1.6x10(-2) mg g(-1) min(-1) for Pb2+, Cd2+, and Zn2+, respectively; and the corresponding rate constants for the SA-modified biomass were 4.0x10(-2), 4.7x10(-2), and 1.7x10(-2) mg g(-1) min(-1), respectively. Thermodynamic considerations indicated a spontaneous exothermic process, which implies that physisorption is the main mechanism in the sorption process.     

Cytochemical location of urease in the cell wall of two different lichen phycobionts

The enzyme urease has been located in the cell wall of recently isolated phycobionts from Evernia prunastri and Xanthoria parietina lichens. Cytochemical detection is achieved by producing a black, electron-dense precipitate of cobalt sulfide proceeding from CO(2) evolved from urea in the presence of cobalt chloride. Cellular fractionation reveals that about 80% of total urease activity was associated to the cell wall on both phycobionts whereas only 20% was recovered as soluble protein.     

Enhanced sorption of Cu2+ and Ni2+ by acid-pretreated Chlorella vulgaris from single and binary metal solutions

The influence of HCl pretreatment (0.1 mM) on sorption ofCu²⁺ and Ni²⁺ by Chlorella vulgariswas tested using single and binary metal solutions. The optimal initial pH forsorption was 3.5 for Cu²⁺ and 5.5 for Ni²⁺. Second orderrate kinetics described well sorption by untreated and acid-pretreated cells.The kinetic constant q_e (metal sorption at equilibrium) for sorptionof test metals from single and binary metal solutions was increased afterpretreatment of the biomass with HCl. The Langmuir adsorption isotherm wasdeveloped for describing the various results for metal sorption. In single metalsolution, acid pretreatment enhanced q_max for Cu²⁺ andNi²⁺ sorption by approximately 70% and 65%, respectively.Cu²⁺ and Ni²⁺ mutually interfered with sorption of theother metal in the binary system. The combined presence of Cu²⁺ andNi²⁺ led to their decreased sorption by untreated biomass by 19% and88%, respectively. However, acid-pretreated biomass decreased Cu²⁺and Ni²⁺ sorption by 15 and 22%, respectively, when both the metalswere present in the solution. The results suggest a reduced mutual interferencein sorption of Cu²⁺ and Ni²⁺ from the binary metal systemdue to the acid pretreatment. Acid-pretreated cells sorbed twice the amount ofCu²⁺ and ten times that of Ni²⁺ than the untreated biomassfrom the binary metal system. Acid pretreatment more effectively enhanced thesorption of Ni²⁺ form the binary metal solution. The total metalsorption by untreated and acid-pretreated biomass depended on theCu²⁺ : Ni²⁺ ratio in the binary metal system. Acidpretreatment of C. vulgaris could be an effective andinexpensive strategy for enhancing Cu²⁺ and Ni²⁺ sorptionfrom single and binary metal solutions.     

Cobalt separation by <Emphasis Type="Italic">Alphaproteobacterium</Emphasis> MTB-KTN90: magnetotactic bacteria in bioremediation

Bioremediation of toxic metals by magnetotactic bacteria and magnetic separation of metal-loaded magnetotactic bacteria are of great interest. This bioprocess technique is rapid, efficient, economical, and environmentally friendly. In this study, cobalt removal potential of a novel isolated magnetotactic bacterium (Alphaproteobacterium MTB-KTN90) as a new biosorbent was investigated. The effects of various environmental parameters in the cobalt removal and the technique of magnetic separation of cobalt-loaded bacterial cells were studied. Cobalt removal by MTB-KTN90 was very sensitive to pH solution; higher biosorption capacity was observed around pH 6.5–7.0. When biomass concentration increased from 0.009 to 0.09 g/l, the biosorption efficiency increased from 13.87 % to 19.22 %. The sorption of cobalt by MTB-KTN90 was rapid during the first 15 min (859.17 mg/g dry weight). With the increasing of cobalt concentrations from 1 to 225 mg/l, the specific cobalt uptake increased. Maximum cobalt removal (1160.51 ± 15.42 mg/g dry weight) took place at optimum conditions; pH 7.0 with initial cobalt concentration of 115 mg/l at 60 min by 0.015 g/l of dry biomass. The results showed maximum values for constants of Langmuir and Freundlich models so far. The biosorption mechanisms were studied with FTIR, PIXE, and FESEM analysis. Cobalt-loaded MTB-KTN90 had ability to separate from solution by a simple magnetic separator. Magnetic response in MTB-KTN90 is due to the presence of unique intracellular magnetic nanoparticles (magnetosomes). The orientation magnetic separation results indicated that 88.55 % of cobalt was removed from solution. Consequently, Alphaproteobacterium MTB-KTN90 as a new biosorbent opens up good opportunities for the magnetic removal of cobalt from the polluted aquatic environments.     

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.     

Cadmium adsorption by non-living biomass of the semi-macroscopic brown alga,Ectocarpus siliculosus,grown in axenic mass culture and localisation of the adsorbed Cd by transmission electron microscopy

Non-living, freeze-dried material of the brown algaEctocarpus siliculosus (Phaeophyceae) demonstrated high equilibrium uptake of Cd from aqueous solutions (Fehrmann & Pohl, 1993). The alga was grown in 250-L photobioreactors under various growth conditions (light, salinity and nutrient concentrations) in order to obtain larger quantities of biomass and to improve its Cd adsorption capacity. To derive further knowledge on the biosorbant phenomenon different adsorption parameters such as pH for the sorption process and kinetics of Cd adsorption were tested. The maximum adsorption capacity of the freeze-dried biomass exceeded 41 mg Cd per g biomass. After repeated addition of low Cd concentrations the maximum adsorption capacity was lower (31.4 mg Cd per g biomass). In comparison with other adsorbing materials (activated carbon, silica gel, siliceous earth)E. siliculosus showed significantly higher adsorption capacity. Desorption of deposited Cd with 0.1 M HCl resulted in no changes of the adsorption capacity through five subsequent adsorption-/desorption-cycles. Hence, driedE. siliculosus appears to be an efficient material for the elimination of Cd from industrial waste water.Transmission electron microscopic investigations showed an electron dense area in the outer surface layers of the cell wall after Cd adsorption indicating the most likely location of Cd fixation.Author for correspondence     

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.     

Biomass digestibility is predominantly affected by three factors of wall polymer features distinctive in wheat accessions and rice mutants

Background

Wheat and rice are important food crops with enormous biomass residues for biofuels. However, lignocellulosic recalcitrance becomes a crucial factor on biomass process. Plant cell walls greatly determine biomass recalcitrance, thus it is essential to identify their key factors on lignocellulose saccharification. Despite it has been reported about cell wall factors on biomass digestions, little is known in wheat and rice. In this study, we analyzed nine typical pairs of wheat and rice samples that exhibited distinct cell wall compositions, and identified three major factors of wall polymer features that affected biomass digestibility.

Results

Based on cell wall compositions, ten wheat accessions and three rice mutants were classified into three distinct groups each with three typical pairs. In terms of group I that displayed single wall polymer alternations in wheat, we found that three wall polymer levels (cellulose, hemicelluloses and lignin) each had a negative effect on biomass digestibility at similar rates under pretreatments of NaOH and H₂SO₄ with three concentrations. However, analysis of six pairs of wheat and rice samples in groups II and III that each exhibited a similar cell wall composition, indicated that three wall polymer levels were not the major factors on biomass saccharification. Furthermore, in-depth detection of the wall polymer features distinctive in rice mutants, demonstrated that biomass digestibility was remarkably affected either negatively by cellulose crystallinity (CrI) of raw biomass materials, or positively by both Ara substitution degree of non-KOH-extractable hemicelluloses (reverse Xyl/Ara) and p-coumaryl alcohol relative proportion of KOH-extractable lignin (H/G). Correlation analysis indicated that Ara substitution degree and H/G ratio negatively affected cellulose crystallinity for high biomass enzymatic digestion. It was also suggested to determine whether Ara and H monomer have an interlinking with cellulose chains in the future.

Conclusions

Using nine typical pairs of wheat and rice samples having distinct cell wall compositions and wide biomass saccharification, Ara substitution degree and monolignin H proportion have been revealed to be the dominant factors positively determining biomass digestibility upon various chemical pretreatments. The results demonstrated the potential of genetic modification of plant cell walls for high biomass saccharification in bioenergy crops.

     

Biosorption of chromium, copper, manganese and zinc by Pseudomonas aeruginosa AT18 isolated from a site contaminated with petroleum

The study describes the sorption of Cr, Cu, Mn and Zn by Pseudomonas aeruginosa AT18 isolated from a site contaminated with petroleum and heavy metals. The concentrations studied were 50, 49, 60 and 70 (mg L(-1)) for Cr, Cu, Mn and Zn, respectively. The solution pH and ionic strength were very important factors in the metal biosorption performance and the biosorption capacity of P. aeruginosa AT18 for Cr3+,Cu2+, Mn2+ and Zn2+. In aqueous solution, the biosorption increased with increasing pH in the range 5.46-7.72. The results obtained in the experimental assays show that P. aeruginosa AT18 has the capacity for biosorption of the metallic ions Cr3+, Cu2+ and Zn2+ in solutions, although its capacity for the sorption of manganese is low (22.39 mg Mn2+/g of biomass) in comparison to the Cr3+, Cu2+ and Zn2+ ions, as shown by the individual analyses. However, 20% of the manganese was removed from an initial concentration of 49.0 mg L(-1), with a Qm value similar to that obtained in solutions containing mixtures of Cr3+, Cu2+, Mn2+and Zn2+. The chromium level sorbed by P. aeruginosa AT18 biomass was higher than that for Cu, Mn and Zn, with 100% removal in the pH range 7.00-7.72 and a Qm of 121.90-200.00 mg of Cr3+/g of biomass. The removal of Cr, Cu and Zn is also a result of precipitation processes.