A comparative study on heavy metal biosorption characteristics of some algae

The biosorption of copper(II), nickel(II) and chromium(VI) from aqueous solutions on dried (Chlorella vulgaris, Scenedesmus obliquus and Synechocystis sp.) algae were tested under laboratory conditions as a function of pH, initial metal ion and biomass concentrations. Optimum adsorption pH values of copper(II), nickel(II) and chromium(VI) were determined as 5.0, 4.5 and 2.0. respectively, for all three algae. At the optimal conditions, metal ion uptake increased with initial metal ion concentration up to 250 mg l⁻¹. Experimental results also showed the influence of the alga concentration on the metal uptake for all the species. Both the Freundlich and Langmuir adsorption models were suitable for describing the short-term biosorption of copper(II), nickel(II) and chromium(VI) by all the algal species.     

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.     

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.     

Complexity and idiosyncrasy in the responses of algae to disturbance in mono- and multi-species assemblages

There is considerable debate about whether stability (e.g. inertia) of an assemblage, or of individuals in an assemblage, is positively associated with the number of species or whether there are idiosyncratic effects of particular species. We assessed the general model that the loss of an individual alga, caused by trampling, is greater in monospecific than in multi-species stands but that the responses of algae are idiosyncratic, depending on the morphology of the species. The experiment was done on conspicuous and dominant algae with different morphology on temperate Australian rocky shores: the fucalean algae Hormosira banksii and Sargassum sp. and the coralline alga Corallina officinalis. We assessed the relative and interactive effects of the extent of trampling (number of paths) and the localised intensity of trampling (number of travels per path) on the three algae. The number of paths trampled (the extent of disturbance) had more impact on each alga than the number of times paths were travelled (the intensity of disturbance). As predicted, H. banksii was most susceptible to trampling at each level than were the coarser algae Sargassum sp. and C. officinalis. There was a consistent trend for each alga to be more inert to trampling when in the presence of the other two species than when in monospecific stands, but this was only statistically significant (P < 0.05) for the softer alga H. banksii. The responses of H. banksii and Sargassum sp. to disturbance seemed, in many cases, to be due to the presence of C. officinalis rather than to "diversity" per se. The relationship between the number of species and stability is complex in intertidal habitats, depending on the species and the combinations of species with which it grows.     

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.     

Biosorption of chromium(VI) using a Sargassum sp. packed-bed column

Chromium(VI) is present in several industrial wastewaters and it can cause health and environmental hazards above certain concentrations. Equilibrium studies have shown the feasibility of using Sargassum sp. algae for chromium removal from aqueous solutions by biosorption. However, for the design and operation of chromium biosorption processes, dynamic flow studies are required. The objective of the study was to examine chromium(VI) removal from an aqueous solution using a packed-bed column with Sargassum sp. algae as a biosorbent. The dynamic behavior of the biosorption column was investigated through experiments and the influence of operating conditions, such as initial chromium concentration, flow rate and amount of biosorbent, on the column removal capacity have been analyzed using the factorial design methodology. The capacity of removal obtained at optimum conditions was 19.06 mg of metal/g biosorbent.     

Comparative study of Cd(II) and Cr(VI) biosorption on Staphylococcus xylosus and Pseudomonas sp. in single and binary mixtures

Biosorption of Cd(II) and Cr(VI) ions in single solutions using Staphylococcus xylosus and Pseudomonas sp., and their selectivity in binary mixtures was investigated. Langmuir and Freundlich models were applied to describe metal biosorption and the influence of pH, biomass concentration and contact time was determined. Maximum uptake capacity of cadmium was estimated to 250 and 278 mg g(-1), whereas that of chromium to 143 and 95 mg g(-1) for S. xylosus and Pseudomonas sp., respectively. In binary mixtures with Cd(II) ions as the dominant species, there is a profound selectivity for cadmium biosorption, reaching 96% and 89% for Pseudomonas sp. and S. xylosus, respectively, at 10 mg l(-1) Cd(II) and 5 mg l(-1) Cr(VI). Interesting, when chromium (VI) ions are the dominant species, there is selectivity towards chromium around 92% with S. xylosus only.     

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.     

A CARD-FISH protocol for the identification and enumeration of epiphytic bacteria on marine algae

A CARD-FISH protocol was developed and applied to analyse surface-associated bacteria on the marine algae Ulva lactuca, Delisea pulchra, Corallina officinalis, Amphiroa anceps, Porphyra sp. and Sargassum linearifolium. The combination of Alexa(546)-labelled tyramide as the reporter molecule with SYBR Green II counterstain allowed for superior detection of the hybridised probe fluorescence against plant tissue from which pigment autofluorescence has been reduced.     

Biosorption of copper(II) and cobalt(II) from aqueous solutions by crab shell particles

Biosorption of each of the heavy metals, copper(II) and cobalt(II) by crab shell was investigated in this study. The biosorption capacities of crab shell for copper and cobalt were studied at different particle sizes (0.456-1.117 mm), biosorbent dosages (1-10 g/l), initial metal concentrations (500-2000 mg/l) and solution pH values (3.5-6) in batch mode. At optimum particle size (0.767 mm), biosorbent dosage (5 g/l) and initial solution pH (pH 6); crab shell recorded maximum copper and cobalt uptakes of 243.9 and 322.6 mg/g, respectively, according to Langmuir model. The kinetic data obtained at different initial metal concentrations indicated that biosorption rate was fast and most of the process was completed within 2h, followed by slow attainment of equilibrium. Pseudo-second order model fitted the data well with very high correlation coefficients (>0.998). The presence of light and heavy metal ions influenced the copper and cobalt uptake potential of crab shell. Among several eluting agents, EDTA (pH 3.5, in HCl) performed well and also caused low biosorbent damage. The biosorbent was successfully regenerated and reused for five cycles.     

Biosorption of hexavalent chromium onto raw and chemically modified Sargassum sp

Hexavalent chromium biosorption by raw algae is always accompanied with significantly high organic leaching. In this study, hydrochloric acid, sodium hydroxide, calcium chloride, formaldehyde, and glutaraldehyde were used for modification of raw Sargassum sp. seaweed (RSW), in order that the modified seaweed (MSW) has a lower organic leaching while the metal biosorption capacity is comparable to the RSW. The result shows that the chemical modification by 0.2% formaldehyde achieves such goals. The biosorption of both RSW and MSW is highly pH dependent. At the optimal pH of 2.0, the maximum biosorption capacities of MSW and RSW are 1.123 and 0.601 mmol g(-1), respectively. The surface treatment improves the reduction capacity of the biosorbents. The instrumental analysis demonstrates that the Cr(VI) biosorption is controlled by redox, ion exchange and coordination reactions, of which alcohol, carboxyl, amino and sulphonic groups play important roles. The complete uptake of hexavalent chromium is achieved in 20 h. The chemical reduction for Cr(VI) to Cr(III) is pH dependent and controls the overall chromium removal kinetics.     

ADSORPTION AND UPTAKE OF COPPER BY THE GREEN ALGA SCENEDESMUS SUBSPICATUS (CHLOROPHYTA)1

Copper (II) accumulation has been investigated in the green alga Scenedesmus subspicatus G. Brinkmann considering both adsorption and uptake kinetics. Experiments were conducted in a Cu- and PH-buffered medium at different free Cu²⁺ concentrations that were neither growth limiting nor toxic. We distinguished between adsorption on the cell surface and intracellular uptake by extracting copper from the cells with EDTA. Data from short-term experiments were compared with data obtained from experiments under steady state conditions. The accumulation of Cu can be described by two processes, an initial fast adsorption occurring within a minute followed by a slower intracellular uptake. Metal uptake followed Michaelis-Menten kinetics and is mediated by two systems, one with low and the other with high affinity. The maximum uptake rates (1.30 × 10^?-¹⁰ mol·[g dry wt algae]^?1· min^?1, 3.67 × 10^?-⁹ mol·[g dry wt algae]^?1·min^?1), and the half-saturation constants (6.84 × 10^?-¹⁴ M, 2.82 × 10^?-¹² M) for the two uptake systems were determined using the Lineweaver-Burk plot. The calculated maximum concentration of binding sites on the surface of the algae is initially higher (9.0 × 10^?-⁶ mol Cu.[g dry wt algae]^?1) than under steady state conditions (2.9 × 10^?-⁶ mol Cu·[g dry wt algae]^?1). This suggests that the initial binding to the algal surface comprises the binding to specific transport ligands as well as to inert adsorption sites. The conditional stability constant of the Cu binding to surface ligands was calculated as log K_Cu= 11.0 at pH 7.9. This freshwater alga has a high ability to accumulate Cu, reflecting its adaptation to the bioavailable concentration of copper.     

Comparative analysis of astaxanthin and its esters in the mutant E1 of Haematococcus pluvialis and other green algae by HPLC with a C30 column

A gradient reversed-phase high-performance liquid chromatography (HPLC) method using a C30 col-umn was developed for the simultaneous determination of astaxanthin, astaxanthin monoesters and astaxanthin diesters in the green algae Chlorococcum sp., Chlorella zofingiensis, Haematococcus plu-vialis and the mutant E1, which was obtained from the mutagenesis of H. pluvialis by exposure to UV-irradiation and ethyl methanesulphonate (EMS) with subsequent screening using nicotine. The re-sults showed that the contents of total astaxanthins including free astaxanthin and astaxanthin esters ranged from 1.4 to 30.9 mg/g dry biomass in these green algae. The lower total astaxanthin levels (< 2 mg/g dry biomass) were detected in the green algae Chlorococcum sp. and C. zofingiensis. The higher total astaxanthin levels (>16 mg/g dry biomass) were found in the green alga H. pluvialis and its mutant E1. It is notable that the mutant E1 is found to have considerably higher amounts of total astaxanthin (30.9 mg/g) as compared to the wild strain of H. pluvialis (16.1 mg/g). This indicates that UV-irradiation and EMS compound mutagenesis with subsequent screening using nicotine is an effective method for breeding of a high-producing astaxanthin strain of H. pluvialis. In addition, the green alga C. zofingien-sis had a remarkably higher percentage of astaxanthin diesters (76.3% of total astaxanthins) and a re-markably lower percentage of astaxanthin monoesters (18.0% of total astaxanthins) in comparison with H. pluvialis (35.5% for diesters and 60.9% for monoesters), the mutant E1 (49.1% and 48.1%) and Chlorococcum sp. (18.0% and 58.6%).     

Utilization of the coconut shell of babaçu (Orbignya sp.) to produce cement-bonded particleboard

The zinc biosorptive capacity of the brown seaweed Sargassum sp. (Phaeophyceae) was studied in the presence or absence of competing calcium ions, using a continuous system with tubular fixed-bed reactors. In order to detect the effect of calcium on zinc biosorption, a 130 mg/l zinc solution was used, and calcium was added at 50-340 mg/l. The potential zinc biosorptive capacity of the biomass was markedly influenced by the presence of ionic calcium. Zinc sorption decreased with increasing calcium concentrations, as expressed by zinc uptake rates. Calcium was effectively recovered only during the initial stages of the process, as expressed by the decrease in its uptake rates. Calcium uptake rates were also much higher than zinc uptake rates, indicating that calcium was preferentially recovered when compared to zinc.     

Copper sorption by native and modified pellets of wood-rotting basidiomycetes

AIMS: The aim of this study was to investigate the biosorption of copper to the pellets of different wood-rotting fungal species. METHODS AND RESULTS: Copper sorption was studied in both batch and column arrangements. The optimum pH for copper sorption was between 3.5 and 4. In 100 mg l(-1) Cu (II), maximum qe values were found for Oudemansiella mucida (8.77 mg g(-1) dry wt), Lepista nuda (6.29 mg g(-1)), Pycnoporus cinnabarinus (5.08 mg g(-1)) and Pleurotus ostreatus (4.77 mg g(-1)). Both biomass yield and specific sorption were influenced by the composition of the fermentation broth. The results of column experiments showed that mycelial pellets of wood-rotting fungi can be considered as promising biosorbent material. CONCLUSIONS: Pellets of wood-rotting fungi showed the same or better copper sorption properties as those previously reported for lower fungi or filamentous bacteria, as well as good mechanical properties.     

Biosorption of copper by marine algae Gelidium and algal composite material in a packed bed column

Marine algae Gelidium and algal composite material were investigated for the continuous removal of Cu(II) from aqueous solution in a packed bed column. The biosorption behaviour was studied during one sorption–desorption cycle of Cu(II) in the flow through column fed with 50 and 25 mg l⁻¹ of Cu(II) in aqueous solution, at pH 5.3, leading to a maximum uptake capacity of ≈13 and 3 mg g⁻¹, respectively, for algae Gelidium and composite material. The breakthrough time decreases as the inlet copper concentration increases, for the same flow rate. The pH of the effluent decreases over the breakthrough time of copper ions, which indicates that ion exchange is one of the mechanisms involved in the biosorption process. Temperature has little influence on the metal uptake capacity and the increase of the ionic strength reduces the sorption capacity, decreasing the breakthrough time. Desorption using 0.1 M HNO₃ solution was 100% effective. After two consecutive sorption–desorption cycles no changes in the uptake capacity of the composite material were observed. A mass transfer model including film and intraparticle resistances, and the equilibrium relationship, for adsorption and desorption, was successfully applied for the simulation of the biosorption column performance.     

Heavy metals removal by the microalga Scenedesmus incrassatulus in continuous cultures

The microalga Scenedesmus incrassatulus was grown under continuous regime in the presence of chromium(VI), cadmium(II) and copper(II), as single metal species and as mixtures of two or three metals, in a laboratory scale system. We used an artificial wastewater with low free ion activities (as determined by MINEQL+) due to the presence of EDTA (a strong chelating agent) but with total concentrations not suitable for acceptable environments. Chromium(VI) and cadmium(II) had positive interaction that increased the removal percentages of both these metals; we could not, however, detect any interaction with copper(II). S. incrassatulus was able to remove all the tested metals to some extent (25-78%), but bivalent metals were not removed as efficiently as reported in batch cultures, probably due to the high pH values there recorded. Chromium(VI) was more efficiently removed in continuous cultures than in batch culture, because the uptake of chromate could be favored by actively growing algae.     

Arsenic-resistant bacteria solubilized arsenic in the growth media and increased growth of arsenic hyperaccumulator Pteris vittata L

The role of arsenic-resistant bacteria (ARB) in arsenic solubilization from growth media and growth enhancement of arsenic-hyperaccumulator Pteris vittata L. was examined. Seven ARB (tolerant to 10 mM arsenate) were isolated from the P. vittata rhizosphere and identified by 16S rRNA sequencing as Pseudomonas sp., Comamonas sp. and Stenotrophomonas sp. During 7-d hydroponic experiments, these bacteria effectively solubilized arsenic from the growth media spiked with insoluble FeAsO? and AlAsO? minerals (from < 5 μg L?1 to 5.04-7.37 mg L?1 As) and enhanced plant arsenic uptake (from 18.1-21.9 to 35.3-236 mg kg?1 As in the fronds). Production of (1) pyochelin-type siderophores by ARB (fluorescent under ultraviolet illumination and characterized with thin layer chromatography) and (2) root exudate (dissolved organic C) by P. vittata may be responsible for As solubilization. Increase in P. vittata root biomass from 1.5-2.2 to 3.4-4.2 g/plant dw by ARB and by arsenic was associated with arsenic-induced plant P uptake. Arsenic resistant bacteria may have potential to enhance phytoremediation of arsenic-contaminated soils by P. vittata.     

Removal of Pb2+ by Biomass of Marine Algae

New biosorbent material derived from ubiquitous marine algae has been examined in packed-bed flow for Pb²⁺ removal through sorption columns. Mixed biomass of marine algae has been used, consisting of representative species of the following algae: Ulva lactuca (green algae), Jania rubens (red algae), and Sargassum asperifolium (brown algae). A mixture of these three species showed a promising removal capacity for Pb²⁺ from aqueous solution. Lead uptake up to 281.8 mg/g dry algal mixture was observed. Equilibrium was achieved after 120 min. No significant effect of changing the flow rate on the removal capacity was noticed. It was found that Langmuir model expresses the system at pH 4. Mineral acids exhibited good elution properties (a mean of 93%) for recovery of sorbed biomass ions as compared with the tested alkalies (about 60%). Received: 21 December 1999 / Accepted: 24 April 2000     

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.