Cadmium removal from simulated wastewater to biomass byproduct of Lentinus edodes

A kind of agricultural waste, the byproduct of brown-rot fungus Lentinus edodes, was used as an efficient biosorbent for the removal of cadmium from water in this paper. The sorption conditions, such as pH, the dose of biomass and the initial concentration of cadmium were examined. Three kinds of adsorption models were applied to simulate the biosorption data. Uptake of cadmium was higher in weak acid condition than in strong acid condition. Nearly no sorption of cadmium occurred when the pH value was lower than 2.5. Biosorption isothermal data could be well simulated by Freundlich model, and then Langmuir and Temkin model. Langmuir simulation of the biosorption showed that the maximum uptake of cadmium was 5.58mmol/g in weak acid condition, which was much higher than many other biosorbents. The exchanged proton was highly related to the uptake of cadmium in weak acid condition. Fourier transform infrared spectrums and energy-dispersive X-ray microanalyzer were used to reveal ion-exchange mechanism between cadmium and the functional groups or participated inorganic metal ions during biosorption.     

Uptake of Cr3+ from aqueous solution by lignite-based humic acids

Humic acid (HA) produced from brown coal, a relatively abundant and inexpensive material is currently being investigated as an adsorbent to remove toxic metals from aqueous solution. The influence of five parameters (contact time, solution pH, initial metal concentration, temperature and amount of adsorbent) on the removal at 20+/-1 degrees C was studied. HAs were prepared from lignites by using alkaline extraction, sedimentation and acidic precipitation. Adsorption equilibrium was achieved in about 60 min for Cr3+ ion. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The maximum adsorption capacity of 0.17 mmol for Ilgin (HA1), 0.29 mmol for Beysehir (HA2) and 0.18 mmol Ermenek (HA3) and 0.17 mmol of Cr3+/g for activated carbon (AC) was achieved, respectively at pH of 4.1. More than 84% of Cr3+ was removed by HA2, 54% by HA3 and 51% by HA1 and 50% by AC from aqueous solution. The adsorption was strongly dependent on pH but independent of ionic strength and metal ions. The adsorption of Cr3+ was higher between pH 4.1 and 5.1 for all HAs and maximum sorption was observed at pH 4.1. The rise in temperature caused a slight decrease in the value of the equilibrium constant (Kc) for the sorption of Cr3+ ion. Complex mechanisms including ion exchange, complexation and adsorption and size exclusion are possible for sorption of Cr3+ ion on HAs.     

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 characteristics of metal ions using degreased coffee beans: adsorption equilibrium of cadmium(II)

The feasibility of using coffee beans after being dripped and degreased (DCB) as an adsorbent for base metals such as copper(II), zinc(II), lead(II), iron(III) and cadmium(II) were examined. The compositions of the DCB were characterized by Fourier transform infrared spectroscopy, scanning electronic micrograph and fluorescent X-ray. It was found that DCB contain sulfur and calcium from the analysis using fluorescent X-ray. The plant cell wall in DCB has the porous structure from the scanning electron microscopy (SEM) analysis, and the specific surface area was determined to be 1.2 m2/g using the specific surface area analyzer. Batch adsorption experiments on DCB were carried out at various pHs in order to elucidate the selectivity of metal ions. All metals were adsorbed at low pH region (3.0-5.0). Of particular interest was the adsorption characteristics of cadmium(II) on DCB. The adsorption isotherm for cadmium(II) at pH 8 fitted with a Langmuir equation to yield an adsorption equilibrium constant of 55.2 mmol dm(-3) and an adsorption capacity of 5.98 x 10(-2) mmol g(-1). The desorption of cadmium(II) was easily achieved over 90% by a single batchwise treatment with an aqueous solution of hydrochloric acid or nitric acid at more than 0.01 mol dm(-3). These results suggested that DCB behaves as a cation exchanger.     

Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass

Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.     

Two metal biosorption of chromium and copper by Ca-loaded Laminaria japonica biomass

Cu and Cr sorption capacities of Ca-loaded Laminaria japonica biomass were studied using an equilibrium methodology and evaluation of the sorption performance, and modeling in a two-metal system was carried out with a modified multi-component Langmuir isotherm. The maximum Cu and Cr uptakes calculated from the Langmuir isotherm were 1.59 mmol/g (10.1 wt.%) and 1.81 mmol/g (9.4 wt.%) at pH 4.5, respectively. The desorption efficiency of the Cr-sorbed L. japonica was approximately 5% for 8 h in the 0.1 N HNO₃ solution, while that of Cu-sorbed L. japonica was more than 99% in the 0.1 N HNO₃ solution. The modified Langmuir model gave the following affinity correlated coefficients: 1.12 for Cu and 7.31 for Cr at pH 4.5. The interference of Cr with Cu biosorptive uptake was assessed by ‘cutting’ the three dimensional uptake isotherm surfaces at constant second-metal final concentrations. Equimolar final equilibrium concentrations of Cu and Cr of 1 mM at pH 4.5 reduced Cu and Cr uptakes by 75.5 and 11.0%, respectively.     

Concurrent sorption of Zn(II), Cu(II) and Co(II) by Oscillatoria angustissima as a function of pH in binary and ternary metal solutions

This paper reports biosorption of Zn(II), Cu(II) and Co(II) onto O. angustissima biomass from single, binary and ternary metal solutions, as a function of pH and metal concentrations via Central Composite Design generated by statistical software package Design Expert 6.0. The experimental design revealed that metal interactions could be best studied at lower pH range i.e. 4.0-5.0, which facilitates adequate availability of all the metal ions. The sorption capacities for single metal decreased in the order Zn(II)>Co(II)>Cu(II). In absence of any interfering metals, at pH 4.0 and an initial metal concentration of 0.5 mM in the solution, the adsorption capacities were 0.33 mmol/g Zn(II), 0.26 mmol/g Co(II) and 0.12 mmol/g Cu(II). In a binary system, copper inhibited both Zn(II) and Co(II) sorption but the extent of inhibition of former was greater than the latter; sorption values being 0.14 mmol/g Zn(II) and 0.27 mmol/g Co(II) at initial Zn(II) and Co(II) concentration of 1.5 mM each, pH 4.0 and 1mM Cu(II) as the interfering metal. Zn(II) and Co(II) were equally antagonistic to each others sorption; Zn(II) and Co(II) sorption being 0.23 and 0.24 mmol/g, respectively, at initial metal concentration of 1.5 mM each, pH 4.0 and 1mM interfering metal concentration. In contrast, Cu(II) sorption remained almost unaffected at lower concentrations of the competing metals. Thus, in binary system inhibition dominance observed was Cu(II)>Zn(II), Cu(II)>Co(II) and Zn(II) approximately Co(II), due to this the biosorbent exhibited net preference/affinity for Cu(II) sorption over Zn(II) or Co(II). Hence, the affinity series showed a trend of Cu(II)>Co(II)>Zn(II). In a ternary system, increasing Co(II) concentration exhibited protection against the inhibitory effect of Cu(II) on Zn(II) sorption. On the other hand, the inhibitory effect of Zn(II) and Cu(II) on Co(II) sorption was additive. The model equation for metal interactions was found to be valid within the design space.     

Equilibrium isotherm studies for the uptake of cadmium and lead ions onto sugar beet pulp

The adsorption of Cd2+ and Pb2+ on sugar beet pulp (SBP), a low-cost material, has been studied. In the present work, the abilities of native (SBP) to remove cadmium (Cd2+) and lead (Pb2+) ions from aqueous solutions were compared. The (SBP) an industrial by product and solid waste of sugar industry were used for the removal of Cd2+ and Pb2+ ions from aqueous water. Batch adsorption studies were carried out to examine the influence of various parameters such as initial pH, adsorbent dose, initial metal ion concentration, and time on uptake. The sorption process was relatively fast and equilibrium was reached after about 70 min of contact. As much as 70-75% removal of Cd2+ and Pb2+ ions for (SBP) are possible in about 70 min, respectively, under the batch test conditions. Uptake of Cd2+ and Pb2+ ions on (SBP) showed a pH-dependent profile. The overall uptake for the (SBP) is at a maximum at pH 5.3 and gives up to 46.1 mg g(-1) for Cd2+ and at pH 5.0 and gives 43.5 mg g(-1) for Pb2+ for (SBP), which seems to be removed exclusively by ion exchange, physical sorption and chelation. A dose of 8 gL(-1) was sufficient for the optimum removal of both the metal ions. The Freundlich represented the sorption data for (SBP). In the presence of 0.1M NaNO3 the level of metal ion uptake was found to reach its maximum value very rapidly with the speed increasing both with the (SPB) concentration and with increasing initial pH of the suspension. The reversibility of the process was investigated. The desorption of Cd2+ and Pb2+ ions which were previously deposited on the (SBP) back into the deionised water was observed only in acidic pH values during one day study period and was generally rather low. The extent of adsorption for both metals increased along with an increase of the (SBP) dosage. (SBP), which is cheap and highly selective, therefore seems to be a promising substrate to entrap heavy metals in aqueous solutions.     

Sorption of Cr(III) onto chelating b-DAEG-sporopollenin and CEP-sporopollenin resins

In the present study, the removal of Cr(III) from aqueous solution was studied using a new chelate-resins (b-DAEG-sporopollenin and CEP-sporopollenin). Mechanisms including ion exchange, complexation and adsorption to the surface are possible in the sorption process. Adsorption analysis results obtained at various concentrations of Cr(III) showed that the adsorption pattern on the resin followed a Langmuir isotherm. Langmuir constant Gamma max and k for Cr(III) were found as 1.23, 84.84 mmol/g for b-DAEG-sporopollenin, 133.33, 10.39 mmol/g for CEP-sporopollenin at 20 +/- 1 degrees C, respectively. In addition, kinetic and thermodynamic parameters such as enthalpy (DeltaH0), free energy (DeltaG0) and entropy (DeltaS0) were calculated and these values show that adsorption of Cr(III) on b-DAEG-sporopollenin and CEP-sporopollenin was an exothermic process and the process of adsorption was favored at high temperatures. Maximum Cr(III) removal was observed near a pH of 6.     

Characterization of Pb<Superscript>2+</Superscript> biosorption from aqueous solution by<Emphasis Type="Italic"> Rhodotorula glutinis</Emphasis>

The yeast Rhodotorula glutinis was examined for its ability to remove Pb(2+) from aqueous solution. Within 10 min of contact, Pb(2+) sorption reached nearly 80% of the total Pb(2+) sorption. The optimum initial pH value for removal of Pb(2+ )was 4.5-5.0. The percentage sorption increased steeply with the biomass concentration up to 2 g/l and thereafter remained more or less constant. Temperature in the range 15-45 degrees C did not show any significant difference in Pb(2+ )sorption by R. glutinis. The light metal ions such as Na(+), K(+), Ca(2+), and Mg(2+) did not significantly interfere with the binding. The Langmuir sorption model provided a good fit throughout the concentration range. The maximum Pb(2+ )sorption capacity q(max) and Langmuir constant b were 73.5 mg/g of biomass and 0.02 l/mg, respectively. The mechanism of Pb(2+) removal by R. glutinis involved biosorption by direct biosorptive interaction with the biomass through ion exchange and precipitation by phosphate released from the biomass.     

Biosorption of cadmium and lead ions by ethanol treated waste baker's yeast biomass

The biosorption of cadmium and lead ions from artificial aqueous solutions using waste baker's yeast biomass was investigated. The yeast cells were treated with caustic, ethanol and heat for increasing their biosorption capacity and the highest metal uptake values (15.63 and 17.49 mg g(-1) for Cd(2+) and Pb(2+), respectively) were obtained by ethanol treated yeast cells. The effect of initial metal concentration and pH on biosorption by ethanol treated yeast was studied. The Langmuir model and Freundlich equation were applied to the experimental data and the Langmuir model was found to be in better correlation with the experimental data. The maximum metal uptake values (qmax, mg g(-1)) were found as 31.75 and 60.24 for Cd(2+) and Pb(2+), respectively. Competitive biosorption experiments were performed with Cd(2+) and Pb(2+) together with Cu(2+) and the competitive biosorption capacities of the yeast biomass for all metal ions were found to be lower than in non-competitive conditions.     

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.     

Characterisation of acidic sites of Pseudomonas biomass capable of binding protons and cadmium and removal of cadmium via biosorption

Summary The ability of Pseudomonas aeruginosa to accumulate Cd(II) ions from wastewater industries was experimentally investigated and mathematically modelled. From the potentiometric titration and non-ideal competitive analysis (NICA) model, it was found that the biomass contains three acidic sites. The values of proton binding (pK _i =1.66±3.26×10⁻³, 1.92±1.63×10⁻⁴ and 2.16±3.79×10⁻⁴) and binding constant of cadmium metal ions (pK _M1=1.99±2.45×10⁻³ and pK _M2=1.67±4.08×10⁻³) on the whole surface of biomass showed that protonated functional groups and biosorption of Cd(II) ions could be attributed to a monodentate binding to one acidic site, mainly the carboxylic group. From the isothermal sorption experimental data and Langmuir model, it was also found that the value of Langmuir equilibrium (pK _f) constant is 2.04±2.1×10⁻⁵ suggesting that the carboxyl group is the main active binding site. In addition, results showed that the maximum cadmium capacity (q _max) and affinity of biomass towards cadmium metal ions (b) at pH 5.1 and 20 min were 96.5±0.06 mg/g and 3.40×10⁻³± 2.10×10⁻³, respectively. Finally, interfering metal ions such as Pb(II), Cu(II), Cr(III), Zn(II), Fe(II), Mn(II), Ca(II) and Mg(II) inhibited Cd(II) uptake. Comparing the biosorption of Cd(II) by various Pseudomonas isolates from contaminated environment samples (soil and sewage treatment plant) showed that maximum capacities and equilibrium times were different, indicating that there was a discrepancy in the chemical composition between biomasses of different strains.     

Preparation and Characterization of Chemically Modified Silk Cotton Hull Activated Carbon and Its Effects on Cd(II) Removal from Aqueous Solutions

The novel biosorbent silk cotton hull, an agrowaste material, has been successfully utilized for the removal of cadmium(II) from aqueous solutions. The adsorption of cadmium onto three kinds of activated biosorbent has been studied: modified by concentrated sulfuric acid alone (AC), a mixture of concentrated sulfuric acid and hydrogen peroxide (AC1), and a mixture of concentrated sulfuric acid and ammonium persulfate (AC2). The adsorption studies were carried out to optimize the process parameters such as pH, adsorbent dosage, contact time, and initial metal ion concentration. Maximum metal removal was observed at pH 7.0 with a contact time of 90 min at stirring speed of 200 rpm with an adsorbent dosage of 4.0 g L^?1. The sorption isotherms were studied using the Langmuir, Freundlich, and Tempkin isotherm models. The maximum adsorption capacities were 100.00, 142.86, and 142.87 mg g^?1 for AC, AC1, and AC2, respectively. Accordingly, the surface modification of the activated carbons AC1 and AC2 enhanced cadmium removal greatly. The experiments demonstrated that the removal of metal ions followed the pseudo-second-order kinetic model. The sorption mechanism is discussed in terms of the activated surface properties. A relationship between the oxygen content and sorption was found in this novel material. Desorption experiments were carried out using hydrochloric acid with a view to generate the spent adsorbent and to recover the adsorbed metal ions.     

Sorption of Cr(VI), Cu(II) and Pb(II) by growing and non-growing cells of a bacterial consortium

This paper reports the sorption of three metallic ions, namely Cr(VI), Cu(II) and Pb(II) in aqueous solution by a consortium culture (CC) comprising an acclimatised mixed bacterial culture collected from point and non-point sources. Metal sorption capability of growing and non-growing cells at initial pH of between 3 and 8 in the 1-100mg/L concentration range were studied based on Q(max) and K(f) values of the Langmuir and linearised Freundlich isotherm models, respectively. Maximal metal loading was generally observed to be dependent on the initial pH. Growing cells displayed significant maximal loading (Q(max)) for Pb(II) (238.09 mg/g) and Cu(II) (178.87 mg/g) at pH 6 and at pH 7 for Cr(VI) (90.91 mg/g) compared to non-growing cells (p < 0.05). At the pH range of 6-8, growing cells showed higher loading capacity compared to non-growing cells i.e. 38-52% for Cr, 17-28% for Cu and 3-17% for Pb. At lower metal concentrations and at more acidic pH (3-4) however, non-growing cells had higher metal loading capacity than growing cells. The metal sorption capacity for both populations were as follows: Pb(II) > Cu(II) > Cr(VI).     

Removal of basic (Methylene Blue) and acid (Egacid Orange) dyes from waters by sorption on chemically treated wood shavings

Spruce wood shavings from Picea abies were used for an adsorptive removal of both basic as well as acid dyes from waters. The sorption properties of the sorbents were modified with HCl, Na(2)CO(3) and Na(2)HPO(4). The treatment of the wood sorbents with alkaline carbonate solution as well as with phosphate solution increased the sorption ability for the basic dye (Methylene Blue), whereas the treatment with mineral acid decreased the sorption ability for Methylene Blue to some extent. The opposite is true for the sorption of the acid dye--Egacid Orange. The maximum sorption capacities estimated from the Langmuir-Freundlich isotherms ranged from 0.060 to 0.165 mmol g(-1) for Methylene Blue, and from 0.045 to 0.513 mmol g(-1) for Egacid Orange. The basic dye sorption decreased at low pH values in accordance with a presupposed ion-exchange mechanism of the sorption. The sorption of acid dye, on the other hand, decreased with increasing pH. The presence of inorganic salts as well as surfactants exhibited only minor effects on the dye sorption.     

Differential pulse polarography: a method of directly measuring uptake of metal ions by live bacteria without separation of biomass and medium

Abstract The technique of differential pulse polarography is shown here for the first time to be applicable to monitoring directly the uptake of metal ions from solution by live bacteria in the chamber of the polarograph. The potential at which the polarographic current peak is observed is characteristic of the metal, whereas peak height is proportional to metal concentration. Adding solutions of Cd(II) or Zn(II) to a suspension of Pseudomonas cepacia in 50 mM Hepes buffer (pH 7.4) in the chamber gave polarographic peaks of lower amplitude than those observed when these metal solutions were added to buffer alone, due to metal binding or uptake by cells. Langmuir plots gave binding capacities of 0.13 and 0.20 mmol metal (Dd or Zn, respectively) per g (dry weight) biomass. Ni(II) uptake was biphasic. Metal uptake increased with pH. The value of polarography for rapid assessment of metal removal by cells and the ability to measure uptake from multi-metal solutions is demonstrated.     

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.