Sorption and desorption of Cd, Cu and Pb using biomass from an eutrophized habitat in monometallic and bimetallic systems.

This work examines the sorption capacity of a natural biomass collected from an irrigation pond. The biomass mainly consisted of a mixture of chlorophyte algae with caducipholic plants. Biosorption experiments were performed in monometallic and bimetallic solutions containing different metals commonly found in industrial effluents (Cd, Cu and Pb). The biosorption process was slightly slower in the binary system comparing with monometallic system which was related to competition phenomena between metal cations in solution. The biosorbent behaviour was quantified by the sorption isotherms fitting the experimental data to mathematical models. In monometallic systems, the Langmuir model showed a better fit with the following sorption order: Cu ~ Pb > Cd; and biomass-metal affinity order: Pb > Cd ~ Cu. In bimetallic systems, the binary-type Langmuir model was used and the sorption order obtained was: Pb ~ Cu > Cd. In addition, the effectiveness of the biomass was investigated in several sorption-desorption cycles using HCl and NaHCO(3). The recovery of metal was higher with HCl than with NaHCO(3), though the sorption uptake of the biomass was sensitively affected by the former desorption agent in subsequent sorption cycles.

Mechanism of adsorption of ferric iron by extracellular polymeric substances (EPS) from a bacterium Acidiphilium sp.

The aim of this study was to assess the sorption of Fe(III) by extracellular polymeric substances (EPS) of the Acidiphilium 3.2Sup(5) bacterium, which has promising properties for use in microbial fuel cells (MFC). The EPS of A. 3.2Sup(5) was extracted using EDTA. The sorption isotherms were determined using aliquots of purified EPS. The exosubstances loaded with metal were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD) and Fourier transform infrared spectroscopy (FTIR). The sorption uptake approaches to 536.1 +/- 26.6 mg Fe(III) (g EPS)(-1) at an initial ferric concentration of 2.0 g l(-1). The sorption of Fe(III) by EPS can be fitted to the Freundlich model. The sorption process produces hydrated iron (III) oxalate [Fe(OH)(C2O4) x 2H2O] by a reversible reaction (log K = 1.06 +/- 0.16), indicating that a shift in the sorption of the cation can be easily achieved. Know the magnitude and form of iron sorption by EPS in MFC can foresee the potential impact on the metabolism of iron-reducing and iron-oxidazing bacteria and, therefore, on the feasibility of the system.

Bio-reduction of Fe(III) ores using three pure strains of Aeromonas hydrophila, Serratia fonticola and Clostridium celerecrescens and a natural consortium.

The present work describes a research approach to the anaerobic bioleaching of Fe(III) ores. Three strains (Serratia fonticola, Aeromonas hydrophila and Clostridium celerecrescens) isolated from an acidic abandoned mine were selected to test their ability to reduce dissimilatory Fe(III). Total iron bio-reduction was achieved after 48 h using either the consortium or the Aeromonas cultures. In the latter case, there was no evidence of precipitates and Fe(II) remained in solution at neutral pH through complex formation with citrate. None of the other cultures tested (mixed culture and the two isolates) exhibited this behaviour. Biotechnologically, this is a very promising result since it obviates the problem associated with undesirable precipitation of iron compounds in Fe(III)-reducing bacterial cultures. The performance of the Aeromonas culture was improved progressively by adaptation to moderately acidic pH values (up to 4.5) and to three different Fe(III)-oxyhydroxides as the sole source of iron: ferrihydrite, hematite and jarosite, commonly found as weathering compounds at mine sites. Dissimilatory Fe(III)-reducers for iron extraction from ores is therefore especially attractive in that acidification of the surrounding area can be minimized.

Studies on sorption, desorption, regeneration and reuse of sugar-beet pectin gels for heavy metal removal.

This work reports the effectiveness of sugar-beet pectin xerogels for the removal of heavy metals (cadmium, lead and copper) after multiple batch sorption-desorption cycles, with and without a gels regeneration step. Metals were recovered from xerogel beads without destroying their sorption capability and the beads were successfully reused (nine cycles) without significant loss in both biosorption capacity and biosorbent mass. Metals uptake levelled off or increased after using a 1M CaCl(2) regeneration step after each desorption. Calcium, as a regenerating agent, increased the stability and reusability of the gels repairing the damage caused by the acid and removing the excess protons after each elution providing new binding sites. Because of their excellent reusability, pectin xerogels are suitable for metal remediation technologies.

Extraction of extracellular polymeric substances from the acidophilic bacterium Acidiphilium 3.2Sup(5).

Extraction of extracellular polymeric substances (EPS) from Acidiphilium 3.2Sup(5) was investigated using five methods: EDTA, NaOH, ion exchange resin, heating and centrifugation. The bacterium studied presents promising application in microbial fuel cells (MFCs). The degree of cellular lysis provoked by each method was determined by UV-visible spectroscopy of cultures before and after EPS extraction. In addition, two electron microscopy techniques (TEM and SEM) were employed to determine the degree of attachment and the growth of the biofilm overtime on two solid supports: carbon fibre cloth and graphite rods. The main constituents of the EPS extracted by all methods were proteins and carbohydrates, as confirmed by FT-IR analysis, showing the major presence of carboxylic, hydroxylic and amino groups. The greater extractions of EPS were obtained using EDTA. This method also produced a less degree of cellular lysis. Furthermore, both the amount and the chemical composition of EPS strongly depended on the extraction method used.

Gold(III) biosorption and bioreduction with the brown alga Fucus vesiculosus.

In this paper, the bioreduction of Au(III) to Au(0) using biomass of the brown alga Fucus vesiculosus was investigated. The recovery and reduction process took place in two stages with an optimum pH range of 4-9 with a maximum uptake obtained at pH 7. In the first stage, an induction period previous to gold reduction, the variation of pH, redox potential and gold concentration in solution was practically negligible and no color change was observed. In the second stage, the gold reduction was followed by a sharp decrease of gold concentration, pH and redox potential of solution and a color change from yellow to reddish purple. Hydroxyl groups present in the algal polysaccharides were involved in the gold bioreduction. Metallic gold was detected as microprecipitates on the biomass surface and in colloidal form as nanoparticles in the solution. Bioreduction with F. vesiculosus could be an alternative and environmentally friendly process that can be used for recovering gold from dilute hydrometallurgical solutions and leachates of electronic scraps, and for the synthesis of gold nanoparticles of different size and shape.

Optimization of the continuous biosorption of copper with sugar-beet pectin gels.

Sugar-beet pectin xerogels obtained from residues of the sugar industry are an adequate material for metal recovery from effluents in continuous systems. The xerogels were used as a biosorbent for copper removal in a fixed-bed column. The performance of the system was evaluated in different experimental conditions: flow rate, bed height, inlet metal concentration and feeding system (drop and reverse). The effect on the biosorption parameters (saturation time, amount of adsorbed and treated metal, column performance and metal uptake) and the shape of the breakthrough curves was determined. The saturation time increased with increasing bed height but decreased with increasing feed flow rate and inlet metal concentration. Preferential flow channels greatly influenced the metal uptake and column performance. Copper was completely desorbed with 0.1M HNO(3). Additionally, the column data fitted both the linear and nonlinear expressions of the Thomas model.

Biosorption of cadmium, lead and copper with calcium alginate xerogels and immobilized Fucus vesiculosus.

This paper determines the effect of immobilized brown alga Fucus vesiculosus in the biosorption of heavy metals with alginate xerogels. Immobilization increased the kinetic uptakes and intraparticle diffusion rates of the three metals. The Langmuir maximum biosorption capacity increased twofold for cadmium, 10 times for lead, and decreased by half for copper. According to this model, the affinity of the metals for the biomass was as follows: Cu>Pb>Cd without alga and Pb>Cu>Cd with alga. FITR confirmed that carboxyl groups were the main groups involved in the metal uptake. Calcium in the gels was displaced by heavy metals from solution according to the "egg-box" model. The restructured gel matrix became more uniform and organized as shown by scanning electron microscopy (SEM) characterization. F. vesiculosus immobilized in alginate xerogels constitutes an excellent biosorbent for cadmium, lead and copper, sometimes surpassing the biosorption performance of alginate alone and even the free alga.

Study of cadmium, zinc and lead biosorption by orange wastes using the subsequent addition method.

The biosorption of several metals (Cd2+, Zn2+ and Pb2+) by orange wastes has been investigated in binary systems. Multicomponent sorption isotherms were obtained using an original procedure, similar to that proposed by Pagnanelli et al. [Pagnanelli, F., Petrangeli, M.P., Toro, L., Trifoni, M., Veglio, F., 2001a. Biosorption of metal ions on Arthrobacter sp.: biomass characterization and biosorption modelling. Environ. Sci. Technol. 34, 2773-2778] for monoelement systems, known as subsequent addition method (SAM). Experimental sorption data were analysed using an extended multicomponent Langmuir equation. The maximum sorption uptake was approximately 0.25mmol/g for the three binary systems studied. The reliability of the proposed procedure for obtaining the equilibrium data in binary systems was verified by means of a statistical F-test.

Characterization of the biosorption of cadmium, lead and copper with the brown alga Fucus vesiculosus.

The recovery of cadmium, lead and copper with the brown alga Fucus vesiculosus was characterized and quantified. The biosorption data fitted the pseudo-second order and Langmuir isotherm models, but did not adjust to the intraparticle diffusion model. The metal uptakes deduced from the pseudo-second order kinetic model and the Langmuir isotherm model followed a similar sequence: Cu>Cd approximately Pb. The Langmuir maximum metal uptakes were: 0.9626 mmol/g, Pb 1.02 mmol/g, and Cu 1.66 mmol/g. According to the equilibrium constants of this isotherm model, the affinity of metals for the biomass followed this order: Pb>Cu>Cd. Biosorption was accomplished by ion exchange between metals in solution and algal protons, calcium and other light metals, and by complexation of the adsorbed metals with algal carboxyl groups. FTIR spectra showed a shift in the bands of carboxyl, hydroxyl and sulfonate groups.

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.

Comparative study of biosorption of heavy metals using different types of algae.

Sorption capacity of six different algae (green, red and brown) was evaluated in the recovery of cadmium, nickel, zinc, copper and lead from aqueous solutions. The optimum sorption conditions were studied for each monometallic system. The optimum pH was 6 for the recovery of Cd, Ni and Zn, and less than 5 for Cu and Pb. The best results were obtained with the lowest biomass concentration used (0.5 g/L). Experimental data fitted a Langmuir model very well according to the following sequence of the sorption values: Pb>Cd> or =Cu>Zn>Ni. The brown algae achieved the lowest metal concentration levels in solution; the best results were obtained with Fucus spiralis. Finally, a software computer program was used to simulate the process by comparison of theoretical with experimental results and show minimum differences between both types of data.

Microbial activity in weathering columns.

The aim of the present work was to evaluate the metabolic activity of the microbial population associated with a pyritic tailing after a column-weathering test. For this purpose, a column 150cm high and 15cm diameter was used. The solid was a tailing with 63.4% pyrite and with minor amounts of Cu, Pb and Zn sulfides (1.4, 0.5 and 0.8%, respectively). The column model was the habitual one for weathering tests: distilled water was added at the top of the column; the water flowed down through tailings and finally was collected at the bottom for chemical and microbiological analysis. Weathering was maintained for 36 weeks. The results showed a significant presence of microbial life that was distributed selectively over the column: sulfur- and iron-oxidizing aerobic bacteria were in the more oxygenated zone; anaerobic sulfur-reducing bacteria were isolated from the samples taken from the anoxic part of the column. Activity testing showed that (oxidizing and reducing) bacteria populations were active at the end of the weathering test. The quality of the water draining from the column was thus the final product of biological oxidation and reduction promoted by the bacteria consortia.

Biosorption of heavy metals by activated sludge and their desorption characteristics.

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.

Biosorption with algae: a statistical review.

The state of the art in the field of biosorption using algae as biomass is reviewed. The available data of maximum sorption uptake (qmax) and biomass-metal affinity (b) for Cd2 +, Cu2 +, Ni2 +, Pb2 + and Zn2 + were statistically analyzed using 37 different algae (20 brown algae, 9 red algae and 8 green algae). Metal biosorption research with algae has used mainly brown algae in pursuit of treatments, which improve its sorption uptake. The information available in connection with multimetallic systems is very poor. Values of qmax were close to 1 mmol/g for copper and lead and smaller for the other metals. Metal recovery performance was worse for nickel and zinc, but the number of samples for zinc was very small. All the metals except lead present a similar affinity for brown algae. The difference in the behavior of lead may be due to a different uptake mechanism. Brown algae stand out as very good biosorbents of heavy metals. The best performer for metal biosorption is lead.

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Gold and silver uptake and nanoprecipitation on calcium alginate beads.

Calcium alginate beads were investigated for their biosorption performance in the removal of gold and silver from aqueous solutions. It was found that uptake capacities were significantly affected by the solution pH, with optimum pH values of 2 and 4 for gold and silver, respectively. Kinetic and isotherm experiments were carried out at the optimum pH. The maximum uptake capacities were 290 mg/g for Au and 52 mg/g for Ag. FTIR analysis indicated that both carboxylic and hydroxylic functional groups in alginate beads are involved in the metal binding and later reduction of gold (+3) and silver (+1) to gold (0) and silver (0). SEM and X-ray diffraction confirmed the formation of gold and silver nanoparticles.

Factors affecting the transformation of a pyritic tailing: scaled-up column tests.

Two different methods for predicting the quality of the water draining from a pyritic tailing are compared; for this, a static test (ABA test) and a kinetic test in large columns were chosen. The different results obtained in the two experimental set-ups show the necessity of being careful in selecting both the adequate predictive method and the conclusions and extrapolations derived from them. The tailing chosen for the weathering tests (previously tested in shake flasks and in small weathering columns) was a pyritic residue produced in a flotation plant of complex polymetallic sulphides (Huelva, Spain). The ABA test was a modification of the conventional ABA test reported in bibliography. The modification consisted in the soft conditions employed in the digestion phase. For column tests, two identical methacrylate columns (150 cm high and 15 cm diameter) were used to study the chemical and microbiological processes controlling the leaching of pyrite. The results obtained in the two tests were very different. The static test predicted a strong potential acidity for the tailing. On the contrary, pH value in the effluents draining from the columns reached values of only 5 units, being the concentration of metals (<600 mg/L) and sulphate ions (<17,000 mg/L) very small and far from the values of a typical acid mine drainage. In consequence, the static test may oversize the potential acidity of the tailing; whereas large columns may be saturated in water, displacing the oxygen and inhibiting the microbial activity necessary to catalyse mineral oxidation.