The removal of Cu(II) from aqueous solutions by Ulothrix zonata

In this work, adsorption of copper(II) ions on alga has been studied by using batch adsorption techniques. The equilibrium biosorption level was determined as a function of contact time at several initial metal ion concentrations. The effect of adsorbent concentration on the amount adsorbed was also investigated. The experimental adsorption data were fitted to the Langmuir adsorption model. The free energy change (deltaG0) for the adsorption process was found to be -12.60 kJ/mol. The results indicated that the biomass of Ulothrix zonata is a suitable biosorbent for both the removal and recovery of heavy metals from wastewater.     

Environmental effects and desorption characteristics on heavy metal removal using carboxylated alginic acid

Effects of ionic strength and organic materials on copper ion uptake capacity using carboxylated alginic acid which showed very high metal ion uptake capacity were investigated. The ionic strength only had a slight effect on the decrease of copper ion uptake capacity regardless of NaCl concentration. And, the effect of organic materials such as NTA (nitrilotriaceticacid) and sodium hypophosphite on the copper ion uptake capacity was negligible. When the lead ion adsorbed on carboxylated alginic acid was desorbed by NTA, which showed high desorption efficiency, the best optimum concentration of NTA was about 0.01 M. Also desorption efficiency decreased, however, concentration factor increased as S/L ratio which is defined as the ratio of adding amount of adsorbed and volume of desorbing agent increased. In sequential adsorption and desorption cycles, the lead uptake capacity on carboxylated alginic acid was relatively maintained through cycles 1-5.     

Biosorption of heavy metals by Fucus spiralis

The sorption uptake of cadmium, nickel, zinc, copper and lead by marine brown alga Fucus spiralis was investigated in bimetallic, trimetallic and multimetallic solutions. The experimental data fitted very well to Langmuir model. In bimetallic systems, the affinity of biomass for lead and copper increased and the sorption uptake of these metals was not affected by increasing concentrations of cadmium, nickel or zinc. However, in solutions with both metals there was a significant mutual decrease of their sorption levels at high concentrations of the other metal. The sorption uptake of cadmium, nickel and copper was investigated in trimetallic aqueous systems. Based on the kinetic parameter b, the affinity of F. spiralis for copper was considerably higher than for cadmium or nickel: bCd=6.39, bNi=1.82 and bCu=17.89. In all tests, the maximum sorption uptake remained practically constant around 1 mmol/g, indicating that the number of active sites on the biomass was limited. Tests with four and five metals showed that copper was preferentially adsorbed. The differences between the experimental sorption data and those given by the chemical speciation program PHREEQCI were negligible. In general, the software used provided satisfactory estimated data for each metal and hence can be a useful tool to predict or simulate the real process.     

Removal of copper ions by the filamentous fungus, Rhizopus oryzae from aqueous solution

Removal of heavy metals present in wastewaters has been a major concern due to their non-biodegradability and toxicity. Removal of copper ion using NaOH treated Rhizopus oryzae biomass was investigated in a batch reactor. The copper uptake exhibited substantial enhancement both in terms of kinetics of uptake as well as the loading capacity. The copper biosorption by viable and pretreated fungal biomass fit well to a Lagergren's pseudo second order reaction in comparison to pseudo first order kinetics. Investigation on effect of pH indicated improved performance in the range of pH 4-6 in alkali treated biomass. Copper uptake exhibited by viable biomass was highest at 21 degrees C, unlike pretreated biomass that showed maximum uptake across the range of temperature 21-55 degrees C. The maximum copper loading capacity of the viable and pretreated biomass according to Langmuir isotherm was 19.4 and 43.7 mg/g, respectively. Distribution coefficient of pretreated biomass showed improvement at lower residual concentration, indicating a change in the nature of binding by the treated biomass. Copper uptake decreased with an increasing dose of biosorbent, although enhancement in the total metal ion removal was observed at higher dose.     

Biosorption of copper by yeasts

Summary The ability to accumulate copper from aqueous solutions was determined with different yeast species. Yeast cells did not show any significant differences in process kinetics. The uptake was very fast and was influenced by environmental factors. The metal-accumulating capacity differed among the tested strains. The yeastsCandida tropicalis andPichia guilliermondii were chosen for extensive research. Cells of the stationary growth phase were able to adsorb a high amount of copper. The uptake capacity decreased with increasing biomass concentration. Copper adsorption obeyed the Freundlich isotherm. Optimal pH range was between 5 and 7. The biomass could be used repeatedly for biosorption after desorption by mineral acids.     

Desorption of Copper from Polyvinyl Alcohol‐Immobilized Seaweed Biomass

The desorption characteristics of copper on biomass of a marine macroalga, Sargassum baccularia, immobilized in polyvinyl alcohol (PVA) gel beads, were investigated using HCl eluting solutions. Both the extent and the rate of desorption were affected by the pH of the eluent. Nearly 91% of the copper initially adsorbed was released back into an HCl solution at pH 1.0 after 40 min of contact time when apparent desorption equilibrium was achieved. When the pH was raised to 2.0, about 81% of the bound copper was desorbed within 120 min of contact time. Apparent desorption rate constants were determined using first‐order desorption models. Very high concentrations of copper in the eluate could be obtained by using small amounts of the HCl eluent. However, this was achieved at the expense of the desorption efficiency. The PVA‐immobilized seaweed biomass beads could be regenerated with HCl solution at pH 1.0 or 2.0 in multiple cycles of copper biosorption‐desorption. Following desorption at pH 1.0 in the first cycle, about 55% of the biosorption capacity of the virgin biomass could be reused in subsequent cycles; in the case of desorption at pH 2.0, about 67% of the original uptake capacity was reusable.     

AMENDMENTS FOR ENHANCING COPPER UPTAKE BY BRASSICA JUNCEA AND LOLIUM PERENNE FROM SOLUTION

Phytoextraction of metals is frequently limited by contaminant bioavailability and plant uptake rates. Chemical amendments can be added to increase the uptake and translocation of metals to aerial biomass. A range of amendments of various types was tested for increasing the copper uptake with the test species Indian mustard and ryegrass. These included citric acid (an organic acid); histidine (an amino acid); ethylenediaminetriacetic acid (EDTA), nitrilotriacetic acid (NTA), and ethelynediaminedisuccinic acid (EDDS) (aminopolycarboxylic acids); rhamnolipid (a biosurfactant); and Triton X-100 (a synthetic surfactant). EDTA was the most effective amendment for enhancing copper uptake and translocation into the shoots of Indian mustard and ryegrass, with respective shoot tissue copper levels of 1230 and 1360 μg-Cu/g-dry weight after 10 d compared to 90 and 220 μg-Cu/g-dry weight, respectively, in the unamended treatments. However, the EDTA application resulted in symptoms of toxicity in both Indian mustard and ryegrass, leading to drastic decreases in biomass yield. The application of high levels (300 mg/L) of the biodegradable chelator EDDS was found to be effective for improving translocation of copper in both species. The NTA addition provided benefits to root and shoot growth, with increased copper translocation to shoot tissue. Tests with biosurfactants and synthetic surfactants indicated detrimental effects on copper uptake, biomass yield, and the translocation of copper from roots to shoots in both plant species.     

Biosorption of Copper(II) by Live and Dried Biomass of the White Rot Fungi Phanerochaete chrysosporium and Funalia trogii

Biosorption is an innovative and alternative technology to remove heavy metal pollutants from aqueous solution using live, inactive and dead biomasses such as algae, bacteria and fungi. In this study, live and dried biomass of Phanerochaete chrysosporium and Funalia trogii was applied as heavy metal adsorbent material. Biosorption of copper(II) cations in aqueous solution by live and dried biomass of Phanerochaete chrysosporium and Funalia trogii was investigated to study the effects of initial heavy metal concentration, pH, temperature, contact time, agitation rate and amount of fungus. Copper(II) was taken up quickly by fungal biomass (live or dried) during the first 15 min and the most important factor which affected the copper adsorption by live and dried biomass was the pH value. An initial pH of around 5.0 allowed for an optimum adsorption performance. Live biomass of two white rot fungi showed a high copper adsorption capacity compared with dried biomass. Copper(II) uptake was found to be independent of temperature in the range of 20–45 °C. The initial metal ion concentration (10–300 mg/L) significantly influenced the biosorption capacity of these fungi. The results indicate that a biosorption as high as 40–60 % by live and dried biomass can be obtained under optimum conditions.     

The effect of tetrathiomolybdate on the metabolism of copper by hepatocytes and fibroblasts

Tetrathiomolybdate (TTM) has been examined for its effect on copper metabolism in mouse hepatocytes in primary culture and human fibroblasts. It decreased the amount of copper inside hepatocytes, decreased the rate of copper uptake by hepatocytes in a concentration dependent manner, and increased the copper efflux from the cells. TTM appeared to remove copper preferentially from the labile pool, but with a lower affinity than cage chelators. In fibroblasts, TTM only had a marginal effect on copper levels below a concentration of 100 microM and had no clear effect on the rate of copper uptake. TTM was not toxic to human fibroblasts, but in some preparations, a concentration of more than 50 microM was toxic to hepatocytes.     

Adsorption of radium-226 by biological origin absorbents

Selected samples of waste microbial biomass used in industrial fermentation processes and wastewater biological treatment plants have been studied for their radium biosorption ability from aqueous solutions. Equilibrium biosorption isotherms have been used to quantify the radium uptake capacity of the various types of biomass which were also compared to two types of activated carbon. Solution pH affected the observed uptake significantly. In general, the biomass types that showed appreciable sorption capacity exhibited maximum uptake between pH 7 and 10. The uptake was reduced considerably at pH 4 and little or no uptake was observed at pH 2. Radium biosorptive uptake capacities of the order of 4.5 x 10(4) nCi/g, at pH 7 and at an equilibrium radium concentration of 1000 pCi/L, were determined for a mixed culture, while the biomass of Penicillium chrysogenum adsorbed 5 x 10(4) nCi/g radium under the same conditions. The highest uptake value for a sample of F-400 granular activated carbon was 3600 nCi/g at pH 7 and 1000 pCi/L radium concentration. The biosorptive radium uptake of microbial biomass is compared to literature values for other types of adsorbents. The most effective biomass types studied exhibited radium removals in excess of 99% of the radium in solution.     

The use of waste biomass of Sargassum sp. for the biosorption of copper from simulated semiconductor effluents

Seaweed Sargassum sp. biomass proved to be useful for the recovery of ionic copper from highly concentrated solutions simulating effluents from semiconductor production. In the case of solutions containing copper in the form of chloride, sulphate and nitrate salts, the best pH for the recovery of copper was 4.5. It was observed that copper biosorption from copper nitrate solutions was higher than the recovery of copper from copper chloride or sulphate solutions. The continuous system used was constituted of four column reactors filled with the biomass of Sargassum sp. and showed high operational stability. Biomass of Sargassum sp. in the reactors was gradually saturated from the bottom to the top of each column reactor. The biomass of Sargassum sp. in the first column was saturated first, followed by a gradual saturation of the remaining columns due to the pre-concentration caused by the biomass in the first column. The biomass of Sargassum in the bioreactors completely biosorbed the ionic copper contained in 63 L of copper sulphate solution, 72 L of copper chloride solution and 72 L of copper nitrate solution, all the solutions containing copper at 500 mg/L. Effluents produced after biosorption presented copper concentrations less than 0.5 mg/L.     

Biosorbents for recovery of metals from industrial solutions

Summary Biosorbent materials are a potential alternative to conventional processes of metal recovery from industrial solutions. Algal biomass ofSargassum natans andAscophyllum nodosum outperformed ion exchange resins in sequestering respectively gold and cobalt from solutions. Non-living biomass ofSaccharomyces cerevisiae andRhizopus arrhizus exhibited higher metal-uptake capacity than the living biomass for the uptake of copper, zinc, cadmium, uranium. The solution pH affected the metal-uptake capacity of the biomass whereas the equilibrium biosorption isotherms were independent of the initial concentration of the metal in the solution. Desorption of the metal from the biosorbent and recycle of the biosorbent have also been demonstrated.     

Metal adsorption by quasi cellulose xanthogenates derived from aquatic and terrestrial plant materials

The FTIR spectra, SEM-EDXA and copper adsorption capacities of the raw plant materials, alkali-treated straws and cellulose xanthogenate derivatives of Eichhornia crassipes shoot, rape straw and corn stalk were investigated. FTIR spectra indicated that of the three plant materials, the aquatic biomass of E. crassipes shoot contained more OH and CO groups which accounted for the higher Cu(2+) adsorption capacities of the raw and alkali treated plant material. SEM-EDXA indicated the incorporation of sulphur and magnesium in the cellulose xanthogenate. The Cu(2+) adsorption capacities of the xanthogenates increased with their magnesium and sulphur contents. However more copper was adsorbed than that can be explained by exchange of copper with magnesium. Precipitation may contribute to the enhanced uptake of copper by the cellulose xanthogenate.     

Identification of the Low Molecular Weight Copper Protein from Copper-intoxicated Mung Bean Plants

Mung bean plants (Wilczek) accumulate increasingly greater amounts of buffer-extractable copper in both their shoots and roots when grown in liquid medium containing greater than 2 micrograms per milliliter copper (31.4 micromolar) as cupric sulfate. This increase in soluble copper is accompanied by an increase in the relative amount of low molecular weight (7,000 to 20,000) macromolecular-bound copper and a decrease in the relative amount of high molecular weight (greater than 20,000) copper. The major low molecular weight copper protein has been isolated from copper-intoxicated mung bean plants by a combination of ammonium sulfate fractionation, gel filtration, and ion exchange chromatography. It was identified as mung bean plastocyanin on the basis of its molecular weight, optical behavior, and amino acid composition. No evidence was found for a low molecular weight copper-binding protein corresponding to mammalian thionein or chelatin.     

Assessment of the metal removal capability of two capsulated cyanobacteria, Cyanospira capsulata and Nostoc PCC7936

Two capsulated, exopolysaccharide-producing cyanobacteria, Cyanospira capsulata and Nostoc PCC7936, were tested with regard to their metal removal capability by using copper as model metal. The experiments, carried out with the sole cyanobacterial biomass suspended in distilled water and confined into small dialysis tubings, showed that C. capsulata biomass is characterized by the best efficiency in metal removal, with a q_max (maximum amount of copper removed per biomass unit) of 96 ± 2 mg Cu(II) removed per g of protein in comparison with the value of 79 ± 3 of Nostoc PCC7936 biomass. The experimental data obtained with both cyanobacterial biomass best fit the Langmuir sorption isotherm. The sorption of copper started from the first minutes of contact with the metal and attained the equilibrium state, when no more copper removal was evident, after 5 and 6 hours, for C. capsulata and Nostoc PCC7936, respectively. The best efficiency in Cu(II) removal was obtained at pH 6.1–6.2, while the presence of Mg²⁺ or Ca²⁺ reduced copper removal capability of both species to 60–70% of their q_max. The results showed that the biomass of C. capsulata and Nostoc PCC7936 possesses a high affinity and a high specific uptake for copper, comparable with the best performances shown by other microbial biomass, and suggest the possibility to use the capsulated trichomes of the two cyanobacteria for the bioremoval of heavy metals from polluted water bodies.     

Optimization of copper sorbing-desorbing cycles with confined cultures of the exopolysaccharide-producing cyanobacterium Cyanospira capsulata

AIM: The aim of this study was to compare the copper removal capability of the exopolysaccharide-producing cyanobacterium Cyanospira capsulata confined into various filtering devices and to assess its reuse for several metal sorbing-desorbing cycles. METHODS AND RESULTS: C. capsulata cultures were confined into three dialysis devices and two hollow fibre systems with different surface to volume ratios. The maximum amount of Cu was removed by the biomass confined into dialysis cassettes, followed by the dialysis tubing systems and by the two hollow fibre devices. The experiments on the sorbing-desorbing cycles showed that, with the most effective desorbing agents, the same biomass can be utilized for eight consecutive sorbing-desorbing cycles. CONCLUSIONS: The efficiency of the metal removal process is directly related to a high surface to volume ratio of the confining system and the biomass can be utilized for multiple sorbing-desorbing cycles without significant loss in the metal removal efficiency. SIGNIFICANCE AND IMPACT OF STUDY: The feasibility of a metal removal process using EPS-producing cyanobacteria confined into filtering devices has been shown, pointing out the potential of this technique for industrial applications in the removal of metals from waste waters or in the recovery of valuable metals from water solutions.     

Removal of copper using marine brown alga, Undaria Pinnatifida modified with oxime

Summary As oxime is selective for Cu²⁺, oxime groups were introduced to the cell wall of alga by glutaraldehyde. Such modified biomass showed high affinity for Cu²⁺, which resulted in the increase of copper sorption capacity about 4.5 times higher than that of natural alga. For pH range from 2.5 to 3.0, only Cu²⁺ were removed by alga biomass modified with oxime, while other heavy metal ions such as Ca²⁺,Cd²⁺,Pb²⁺ were not adsorbed. By changing pH, selective recovery of Cu²⁺ was achieved.     

Accumulation of heavy-metal ions by Zoogloea ramigera

Biomass has been produced from glucose using the organism Zoogloea ramigera 115. This biomass has been used to remove copper, cadmium, and uranyl ions from water solutions. The metal uptake was studied with two different methods: either by spectrophotometric measurements on the solutions after flocculation or by potentiometric measurements with amalgam electrodes in order to follow the entire complex formation. The metal-biopolymer interaction in 0.1M NaClO(4) is practically the same as when no neutral salt is added. The metal uptake is dependent on pH and is selective. A reversible process suitable for metal complexation is described.     

Total internal reflection/fluorescence photobleaching recovery study of serum albumin adsorption dynamics.

The total internal reflection/fluorescence photobleaching recovery (TIR/FPR) technique (Thompson et al. 1981. Biophys. J. 33:435) is used to study adsorbed bovine serum albumin dynamics at a quartz glass/aqueous buffer interface. Adsorbed fluorescent labeled protein is bleached by a brief flash of the evanescent wave of a focused totally internally reflected laser beam. The rates of adsorption/desorption and surface diffusion determine the subsequent fluorescence recovery. The protein surface concentration is low enough to be proportional to the observed fluorescence and high enough to insure that the observed recovery rates arise mainly from adsorbed rather than bulk protein dynamics. The photobleaching recovery curves for rhodamine-labeled bovine serum albumin reveal both an irreversibly bound state and a multiplicity of reversibly bound states. The relative amount of reversible to irreversible adsorption increases with increasing bulk protein concentration. Since the adsorbed protein concentration appears to be too high to pack into a homogeneous surface monolayer, the wide range of desorption rates possibly results from multiple layers of protein on the surface. Comparison of the fluorescence recovery curves obtained with various focused laser beam widths suggests that some of the reversibly bound bovine serum albumin molecules can surface diffuse. Aside from their relevance to the surface chemistry of blood, these results demonstrate the feasibility of the TIR/FPR technique for measuring molecular dynamics on solid surfaces.