Application of a novel phyco-composite biosorbent for the biotreatment of aqueous medium polluted with manganese ions

A composite phyco-biomass including four different marine macroalgae species (Chaetomorpha sp., Polysiphonia sp., Ulva sp., and Cystoseira sp.) was evaluated as a novel biosorbent for the biosorption of manganese ions from aqueous solution. The experimental studies were performed to optimize the operational factors including solution pH, biosorbent amount, initial manganese concentration, and reaction time in a batch-mode biosorption system. The removal yield of the biosorbent for manganese ions increased with increasing pH, manganese ion concentration, and reaction time, while it decreased as the biosorbent dose increased. The obtained kinetic data indicated that the removal of manganese ions by the biosorbent was best described by the pseudo-second-order model and the pore diffusion also contributed to the biosorption process. The results of isotherm and thermodynamic studies showed that the Freundlich model represented the biosorption equilibrium data well and this biotreatment system was feasible, spontaneous, and physical. The maximum manganese uptake capacity of used biosorbent was found to be 55.874 mg g^?1. Finally, a single-stage batch manganese biosorption system was designed and its kinetic performance was evaluated. All these findings revealed that the prepared composite macroalgae biosorbent has a fairly good potential for the removal of manganese ions from the aqueous medium.     

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.     

A natural macroalgae consortium for biosorption of copper from aqueous solution: Optimization,modeling and design studies

In this study, the capacity of a natural macroalgae consortium consisting of Chaetomorpha sp., Polysiphonia sp., Ulva sp. and Cystoseira sp. species for the removal of copper ions from aqueous environment was investigated at different operating conditions, such as solution pH, copper ion concentration and contact time. These environmental parameters affecting the biosorption process were optimized on the basis of batch experiments. The experimentally obtained data for the biosorption of copper ions onto the macroalgae-based biosorbent were modeled using the isotherm models of Freundlich, Langmuir, Sips and Dubinin–Radushkevich and the kinetic models of pseudo-first-order, pseudo-second-order, Elovich and Weber and Morris. The pseudo-first-order and Sips equations were the most suitable models to describe the copper biosorption from aqueous solution. The thermodynamic data revealed the feasibility, spontaneity and physical nature of biosorption process. Based on the data of Sips isotherm model, the biosorption capacity of biosorbent for copper ions was calculated as 105.370 mg g^?1 under the optimum operating conditions. A single-stage batch biosorption system was developed to predict the real-scale-based copper removal performance of biosorbent. The results of this investigation showed the potential utility of macroalgae consortium for the biosorption of copper ions from aqueous medium.     

An ecofriendly approach for bioremediation of contaminated water environment: Potential contribution of a coastal seaweed community to environmental improvement

High levels of heavy metals like copper ions in many industrial based effluents lead to serious environmental and health problems. Biosorption is a potential environmental biotechnology approach for biotreatment of aquatic sites polluted with heavy metal ions. Seaweeds have received great attention for their high bioremediation potential in recent years. However, the co-application of marine macroalgae for removal of heavy metals from wastewater is very limited. Thus, for the first time in literature, a coastal seaweed community composed of Chaetomorpha sp., Polysiphonia sp., Ulva sp. and Cystoseira sp. species was applied to remove copper ions from synthetic aqueous medium in this study. The biosorption experiments in batch mode were conducted to examine the effects of operating variables including pH, biosorbent amount, metal ion concentration and contact time on the biosorption process. The biosorption behavior of biosorbent was described by various equilibrium, kinetic and thermodynamic models. The biosorption of copper ions was strongly influenced by the operating parameters. The results indicated that the equilibrium data of biosorption were best modeled by Sips isotherm model. The values of mean free energy of biosorption computed from Dubinin-Radushkevich isotherm model and the standard Gibbs free energy change indicated a feasible, spontaneous and physical biotreatment system. The pseudo-second-order rate equation successfully defined the kinetic behavior of copper biosorption. The pore diffusion also played role in the control of biosorption process. The maximum copper uptake capacity of biosorbent was found to be greater than those of many other biosorbents. The obtained results revealed that this novel biosorbent could be a promising material for copper ion bioremediation implementations.     

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.     

Biosorption of Nickel(II) from aqueous solution by the fungal mat of Trametes versicolor (rainbow) biomass: equilibrium, kinetics, and thermodynamic studies

This study investigates the equilibrium, kinetics and thermodynamics of Nickel(II) biosorption from aqueous solution by the fungal mat of Trametes versicolor (rainbow) biomass. The optimum biosorption conditions like pH, contact time, biomass dosage, initial metal ion concentration and temperaturewere determined in the batch method. The biosorbent was characterized by FTIR, SEM and BET surface area analysis. The experimental data were analyzed in terms of pseudo-first-order, pseudo-secondorder and intraparticle diffusion kinetic models, further it was observed that the biosorption process of Ni(II) ions closely followed pseudo-second-order kinetics. The equilibrium data of Ni(II) ions at 303, 313, and 323 K were fitted to the Langmuir and Freundlich isotherm models. Langmuir isotherm provided a better fit to the equilibrium data andthe maximum monolayer biosorption capacity of the T. versicolor(rainbow) biomass for Ni(II) was 212.5 mg/g at pH 4.0. The calculated thermodynamic parameters, ΔG^○, ΔH^○, and ΔS^○, demonstrated that the biosorption of Ni(II) ions onto the T. versicolor (rainbow) biomass was feasible, spontaneous and endothermic at 303 ～ 323 K. The performance of the proposed fungal biosorbent was also compared with that of many other reported sorbents for Nickel(II) removal and it was observed that the proposed biosorbent is effective in terms of its high sorption capacity.     

Arthrospira (Spirulina) platensis: An effective biosorbent for nutrients

Arthrospira (Spirulina) platensis was tested for biosorption properties. Preliminary experiments concerning biosorption kinetics were performed on Cr(III) ions. Equilibrium of biosorption was tested for Cr(III), Mn(II) and Mg(II) ions, since these elements are crucial for animals with metabolic disorders. In our study, Spirulina was proposed as a feed additive for animals suffering from diseases characterized by insulin dysregulation, abnormal adipose distribution and a high risk for laminitis. Maximum biosorption capacity of A. platensis, determined from Langmuir equation, was 45.2 for Cr(III), 44.3 for Mn(II) and 42.0 mg/g for Mg(II) ions. Biosorption of Mg(II) ions by microalga has never been studied so far. Finally, the raw and enriched microalgal biomass was examined by ICP-OES to determine its multielamental analysis before and after biosorption, FTIR to indicate functional groups that participated in biosorption and SEM-EDX to illustrate the binding of metal ions on the surface of algal biomass. ICP-OES showed that the content of elements significantly increased in the enriched A. platensis. FTIR spectroscopy evidenced that biosorption of metal ions was mainly due to carboxylate groups present on the microalgal cell wall. SEM analysis clearly showed that biosorption occurred. Arthrospira platensis turned out to be a good biosorbent of metal ions.     

Copper biosorption on Lyngbya putealis: Application of response surface methodology (RSM)

The potential use of biosorbent prepared from an indigenously isolated cyanobacterium, Lyngbya putealis, for the removal of copper from aqueous solution has been investigated under optimized conditions in this study. Batch mode experiments were performed to determine the adsorption equilibrium and kinetic behavior of copper in aqueous solution allowing the computation of kinetic parameters and maximum metal adsorption capacity. Influences of other parameters like initial metal ion concentration (10-100 mg l⁻¹), pH (2-8) and biosorbent dose (0.1-1.0 g/100 ml) on copper adsorption were also examined, using Box-Behnken design matrix. Very high regression coefficient between the variables and the response (R² = 0.9533) indicates excellent evaluation of experimental data by second order polynomial regression model. The response surface method indicated that 40-50 mg l⁻¹ initial copper concentration, 6.0-6.5 pH and biosorbent dose of 0.6-0.8 g/100 ml were optimal for biosorption of copper by biosorbent prepared from L. putealis. On the basis of experimental results and model parameters, it can be inferred that the biosorbent which has quite high biosorption capacity can be utilized for the removal of copper from aqueous solution.     

Immobilization of blue green microalgae on loofa sponge to biosorb cadmium in repeated shake flask batch and continuous flow fixed bed column reactor system

Summary An indigenous strain of blue green microalga, Synechococcus sp., isolated from wastewater, was immobilized onto loofa sponge discs and investigated as a potential biosorbent for the removal of cadmium from aqueous solutions. Immobilization has enhanced the sorption of cadmium and an increase of biosorption (21%) at equilibrium was noted as compared to free biomass. The kinetics of cadmium biosorption was extremely rapid, with (96%) of adsorption within the first 5 min and equilibrium reached at 15 min. Increasing initial pH or initial cadmium concentration resulted in an increase in cadmium uptake. The maximum biosorption capacity of free and loofa immobilized biomass of Synechococcus sp. was found to be 47.73 and 57.76 mg g⁻¹ biomass respectively. The biosorption equilibrium was well described by Langmuir adsorption isotherm model. The biosorbed cadmium was desorbed by washing the immobilized biomass with dilute HCl (0.1 M) and desorbed biomass was reused in five biosorption–desorption cycles without an apparent decrease in its metal biosorption capacity. The metal removing capacity of loofa immobilized biomass was also tested in a continuous flow fixed-bed column bioreactor and was found to be highly effective in removing cadmium from aqueous solution. The results suggested that the loofa sponge-immobilized biomass of Synechococcus sp. could be used as a biosorbent for an efficient removal of heavy metal ions from aqueous solution.     

栅藻对水环境中镍的累积效应与机理分析

对不同Scenedesmus品种的藻细胞从含镍水溶液 (10mg/L)中累积金属镍的能力进行了分析 ,结果表明 :藻细胞对镍的生物累积量表现出明显的品种差异性。ScenedesmusquadricaudaFACHB 4 4和ScenedesmusquadricaudaFACHB 5 0 6表现出很强的累积能力 (累积量达到 5～ 6mgNi /g干重 ) ,而Scenedesmussp .FACHB 4 16和Scenedesmussp .FACHB 4 89在相同条件对金属镍累积量要少得多 (1～ 1.5mgNi /g干重 )。这种差异可能与不同品种藻细胞间的形态结构和生理特性是相关的。对S .quadricaudaFACHB 4 4重金属抗性和累积能力进一步的分析表明 ,S .quadricaudaFACHB 4 4用于含镍重金属废水处理是非常有效的 ,在高浓度 (10 0mg/L)的镍溶液中 ,藻细胞的最大累积量能达到 (2 6 .7mgNi/g干重 )。对该藻细胞镍累积动力学分析发现 :藻细胞对镍的生物累积包括一个快速的被动吸附过程 (5min ,结合 70 %的镍 )和一个缓慢的耗能累积过程 (2～ 3h时间内的累积量占总量的 2 0 %～ 30 % )。与其他藻类相比 ,S .quadricaudaFACHB 4 4对水溶液中镍的耗能累积量明显高于其他藻类。透射电子显微镜(TEM)和X射线能谱 (EDX)分析结果均表明 ,藻细胞耗能累积的镍主要集中在原生质体中 ,尤以淀粉粒和染色质中为多。     

Adsorptive removal of copper and nickel ions from water using chitosan coated PVC beads

A new biosorbent was developed by coating chitosan, a naturally and abundantly available biopolymer, on to polyvinyl chloride (PVC) beads. The biosorbent was characterized by FTIR spectra, porosity and surface area analyses. Equilibrium and column flow adsorption characteristics of copper(II) and nickel(II) ions on the biosorbent were studied. The effect of pH, agitation time, concentration of adsorbate and amount of adsorbent on the extent of adsorption was investigated. The experimental data were fitted to Langmuir and Freundlich adsorption isotherms. The data were analyzed on the basis of Lagergren pseudo first order, pseudo-second order and Weber-Morris intraparticle diffusion models. The maximum monolayer adsorption capacity of chitosan coated PVC sorbent as obtained from Langmuir adsorption isotherm was found to be 87.9 mg g(-1) for Cu(II) and 120.5 mg g(-1) for Ni(II) ions, respectively. In addition, breakthrough curves were obtained from column flow experiments. The experimental results demonstrated that chitosan coated PVC beads could be used for the removal of Cu(II) and Ni(II) ions from aqueous medium through adsorption.     

Biosorption of Acid Black 172 and Congo Red from aqueous solution by nonviable Penicillium YW 01: Kinetic study, equilibrium isotherm and artificial neural network modeling

The main objective of this work was to investigate the biosorption performance of nonviable Penicillium YW 01 biomass for removal of Acid Black 172 metal-complex dye (AB) and Congo Red (CR) in solutions. Maximum biosorption capacities of 225.38 and 411.53 mg g⁻¹ under initial dye concentration of 800 mg L⁻¹, pH 3.0 and 40 °C conditions were observed for AB and CR, respectively. Biosorption data were successfully described with Langmuir isotherm and the pseudo-second-order kinetic model. The Weber-Morris model analysis indicated that intraparticle diffusion was the limiting step for biosorption of AB and CR onto biosorbent. Analysis based on the artificial neural network and genetic algorithms hybrid model indicated that initial dye concentration and temperature appeared to be the most influential parameters for biosorption process of AB and CR onto biosorbent, respectively. Characterization of the biosorbent and possible dye-biosorbent interaction were confirmed by Fourier transform infrared spectroscopy and scanning electron microscopy.     

Fixed-bed column studies on a modified chitosan hydrogel for detoxification of aqueous solutions from copper (II)

A new efficient, low cost chitosan based biosorbent was successfully prepared and employed for the biosorption of copper ions from an aqueous solution using a fixed bed column. Pyromellitic dianhydride crosslinked chitosan as the new adsorbent was characterized by SEM, FTIR spectroscopy, X-ray diffraction, thermogravimetric analysis and solid state (13)C NMR analysis. Scanning electron microscopy coupled with an X-ray energy dispersed analysis for the copper-equilibrated biomass confirmed the presence of Cu(II) ions on the surface of the hydrogel. Thermogravimetric analysis showed a significant improvement in the thermal stability of the new hydrogel compared to pure chitosan. Kinetic models were applied to predict the breakthrough curves. This study shows that the prepared hydrogel based on modified chitosan could be utilized as an efficient bioadsorbent for the removal of copper ions from wastewater.     

The biosorption of heavy metals from aqueous solution by Spirogyra and Cladophora filamentous macroalgae

The aim of this research was to develop a low cost adsorbent for wastewater treatment. The prime objective of this study was to search for suitable freshwater filamentous algae that have a high heavy metal ion removal capability. This study evaluated the biosorption capacity from aqueous solutions of the green algae species, Spirogyra and Cladophora, for lead (Pb(II)) and copper (Cu(II)). In comparing the analysis of the Langmuir and Freundlich isotherm models, the adsorption of Pb(II) and Cu(II) by these two types of biosorbents showed a better fit with the Langmuir isotherm model. In the adsorption of heavy metal ions by these two types of biosorbents, chemical and physical adsorption of particle surfaces was perhaps more significant than diffusion and adsorption between particles. Continuous adsorption-desorption experiments discovered that both types of biomass were excellent biosorbents with potential for further development.     

Biosorption characteristics of Aspergillus flavus biomass for removal of Pb(II) and Cu(II) ions from an aqueous solution

The Pb(II) and Cu(II) biosorption characteristics of Aspergillus flavus fungal biomass were examined as a function of initial pH, contact time and initial metal ion concentration. Heat inactivated (killed) biomass was used in the determination of optimum conditions before investigating the performance of pretreated biosorbent. The maximum biosorption values were found to be 13.46 +/- 0.99 mg/g for Pb(II) and 10.82 +/- 1.46 mg/g for Cu(II) at pH 5.0 +/- 0.1 with an equilibrium time of 2 h. Detergent, sodium hydroxide and dimethyl sulfoxide pretreatments enhanced the biosorption capacity of biomass in comparison with the heat inactivated biomass. The biosorption data obtained under the optimum conditions were well described by the Freundlich isotherm model. Competitive biosorption of Pb(II) and Cu(II) ions was also investigated to determine the selectivity of the biomass. The results indicated that A. flavus is a suitable biosorbent for the removal of Pb(II) and Cu(II) ions from aqueous solution.     

Biosorption behaviors of biosorbents based on microorganisms immobilized by Ca-alginate for removing lead (II) from aqueous solution

Multiple microorganisms directly or treated with NaOH were immobilized by using Ca-alginate embedding to form biosorbents I and II, successively. The biosorption behaviors of biosorbents I and II for Pb(II) from aqueous solution were investigated in a batch system. Effects of solution pH, initial metal concentration, biosorbent dosage, contact time, temperature, and ionic strength on the adsorption process were considered to study the biosorption equilibrium, kinetics, thermodynamics, and mechanism of Pb(II) ion adsorption on the 2 types of biosorbents. The results showed that the adsorption capacity of biosorbent II for Pb(II) was higher than that of biosorbent I, and biosorbent II had a faster adsorption rate for Pb(II) ions. According to FTIR spectra, the carboxyl, amine, and hydroxyl groups on the biomass surface were involved in the biosorption of Pb(II). EDX analysis showed that ion exchange may be involved in the biosorption process, and the morphology observed by SEM micrograph of biosorbent I was completely different from that of biosorbent II. Desorption and regeneration experiments showed that the 2 types of biosorbents could be reused for 3 biosorption-desorption cycles without significant loss of their initial biosorption capacities.     

Biosorption of three textile dyes from contaminated water by filamentous green algal Spirogyra sp.: Kinetic,isotherm and thermodynamic studies

A freshwater filamentous green alga Spirogyra sp. was used as an inexpensive and efficient biosorbent for the removal of C.I. Acid Orange 7 (AO7), C.I. Basic Red 46 (BR46) and C.I. Basic Blue 3 (BB3) dyes from contaminated water. The effects of various physico–chemical parameters on dye removal efficiency were investigated, e.g. contact time, pH, initial dyes concentration, the amount of alga, temperature and biosorbent particle size. Dyes biosorption was a quick process and reactions reached to equilibrium conditions within 60 min. The biosorption capacity of three dyes onto alga was found in the following order: BR46 > BB3> AO7. The values of thermodynamic parameters, including ΔG, ΔH and ΔS, indicated that the biosorption of the dyes on the dried Spirogyra sp. biomass was feasible, spontaneous and endothermic. The pseudo-first order, pseudo-second order and the intraparticle diffusion models were applied to the experimental data in order to kinetically describe the removal mechanism of dyes, with the second one showing the best fit with the experimental kinetic biosorption data (R² = 0.99). It was also found that the adsorption process followed the Freundlich isotherm model with the highest value of correlation coefficients (0.99) and the biosorption capacity being estimated to be 13.2, 12.2 and 6.2 mg g⁻¹ for BR46, BB3 and AO7, respectively.     

Nickel(II) biosorption by <Emphasis Type="Italic">Rhodotorula glutinis</Emphasis>

The present study reports the feasibility of using Rhodotorula glutinis biomass as an alternative low-cost biosorbent to remove Ni(II) ions from aqueous solutions. Acetone-pretreated R. glutinis cells showed higher Ni(II) biosorption capacity than untreated cells at pH values ranging from 3 to 7.5, with an optimum pH of 7.5. The effects of other relevant environmental parameters, such as initial Ni(II) concentration, shaking contact time and temperature, on Ni(II) biosorption onto acetone-pretreated R. glutinis were evaluated. Significant enhancement of Ni(II) biosorption capacity was observed by increasing initial metal concentration and temperature. Kinetic studies showed that the kinetic data were best described by a pseudo-second-order kinetic model. Among the two-, three-, and four-parameter isotherm models tested, the Fritz-Schluender model exhibited the best fit to experimental data. Thermodynamic parameters (activation energy, and changes in activation enthalpy, activation entropy, and free energy of activation) revealed that the biosorption of Ni(II) ions onto acetone-pretreated R. glutinis biomass is an endothermic and non-spontaneous process, involving chemical sorption with weak interactions between the biosorbent and Ni(II) ions. The high sorption capacity (44.45 mg g⁻¹ at 25°C, and 63.53 mg g⁻¹ at 70°C) exhibited by acetone-pretreated R. glutinis biomass places this biosorbent among the best adsorbents currently available for removal of Ni(II) ions from aqueous effluents.     

Copper removal by algae Gelidium, agar extraction algal waste and granulated algal waste: kinetics and equilibrium

Biosorption of copper ions by an industrial algal waste, from agar extraction industry has been studied in a batch system. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction, and the industrial waste immobilized with polyacrylonitrile (composite material). The effects of contact time, pH, ionic strength (IS) and temperature on the biosorption process have been studied. Equilibrium data follow both Langmuir and Langmuir-Freundlich models. The parameters of Langmuir equilibrium model were: q(max)=33.0mgg(-1), K(L)=0.015mgl(-1); q(max)=16.7mgg(-1), K(L)=0.028mgl(-1) and q(max)=10.3mgg(-1), K(L)=0.160mgl(-1) respectively for Gelidium, algal waste and composite material at pH=5.3, T=20 degrees C and IS=0.001M. Increasing the pH, the number of deprotonated active sites increases and so the uptake capacity of copper ions. In the case of high ionic strengths, the contribution of the electrostatic component to the overall binding decreases, and so the uptake capacity. The temperature has little influence on the uptake capacity principally for low equilibrium copper concentrations. Changes in standard enthalpy, Gibbs energy and entropy during biosorption were determined. Kinetic data at different solution pH (3, 4 and 5.3) were fitted to pseudo-first-order and pseudo-second-order models. The adsorptive behaviour of biosorbent particles was modelled using a batch reactor mass transfer kinetic model, which successfully predicts Cu(II) concentration profiles.     

Extra and Intracellular Synthesis of Nickel Oxide Nanoparticles Mediated by Dead Fungal Biomass

The use of dead biomass of the fungus Hypocrea lixii as a biological system is a new, effective and environmentally friendly bioprocess for the production and uptake of nickel oxide nanoparticles (NPs), which has become a promising field in nanobiotechnology. Dead biomass of the fungus was successfully used to convert nickel ions into nickel oxide NPs in aqueous solution. These NPs accumulated intracellularly and extracellularly on the cell wall surface through biosorption. The average size, morphology and location of the NPs were characterized by transmission electron microscopy, high-resolution transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The NPs were mainly spherical and extra and intracellular NPs had an average size of 3.8 nm and 1.25 nm, respectively. X-ray photoelectron spectroscopy analysis confirmed the formation of nickel oxide NPs. Infrared spectroscopy detected the presence of functional amide groups, which are probable involved in particle binding to the biomass. The production of the NPs by dead biomass was analyzed by determining physicochemical parameters and equilibrium concentrations. The present study opens new perspectives for the biosynthesis of nanomaterials, which could become a potential biosorbent for the removal of toxic metals from polluted sites.