Copper Biosorption by Spent Coffee Ground: Equilibrium,Kinetics, and Mechanism

The potential use of spent coffee ground (SCG) for the removal of copper has been investigated as a low‐cost adsorbent for the biosorption of heavy metals. Adsorption batch experiments were conducted to determine isotherms and kinetics. The biosorption equilibrium data were found to fit well the Freundlich model and an experimental maximum biosorption capacity of copper ions 0.214 mmol/g was achieved. The biosorption kinetics of SCG was studied at different adsorbate concentrations (0.1–1.0 mM) and stirring speeds (100–400/min). The results showed an increase in the copper ion uptake with raising the initial metal concentration and the kinetic data followed the pseudo‐second order rate expression. The effect of stirring speed was a significant factor for the external mass transfer resistance at 100/min and coefficients were estimated by the Mathews and Weber model. Biosorption of copper ions onto SCG was observed to be related mainly with the release of calcium and hydrogen ions suggesting that biosorption performance by SCG can be attributed to ion‐exchange mechanism with calcium and hydrogen ions neutralizing the carboxyl and hydroxyl groups of the biomass.     

Biosorption of Cd(II) and Zn(II) by Nostoc commune: Isotherm and Kinetics Studies

In this study, Nostoc commune (cyanobacterium) was used as an inexpensive and efficient biosorbent for Cd(II) and Zn(II) removal from aqueous solutions. The effect of various physicochemical factors on Cd(II) and Zn(II) biosorption such as pH 2.0–7.0, initial metal concentration 0.0–300 mg/L and contact time 0–120 min were studied. Optimum pH for removal of Cd(II) and Zn(II) was 6.0, while the contact time was 30 min at room temperature. The nature of biosorbent and metal ion interaction was evaluated by infrared (IR) technique. IR analysis of bacterial biomass revealed the presence of amino, carboxyl, hydroxyl, and carbonyl groups, which are responsible for biosorption of Cd(II) and Zn (II). The maximum biosorption capacities for Cd(II) and Zn(II) biosorption by N. commune calculated from Langmuir biosorption isotherm were 126.32 and 115.41 mg/g, respectively. The biosorption isotherm for two biosorbents fitted well with Freundlich isotherm than Langmuir model with correlation coefficient (r² < 0.99). The biosorption kinetic data were fitted well with the pseudo‐second‐order kinetic model. Thus, this study indicated that the N. commune is an efficient biosorbent for the removal of Cd(II) and Zn(II) from aqueous solutions.     

Biosorption of heavy metals in polluted water,using different waste fruit cortex

The biosorption capacity of different cortex fruit wastes including banana (Musa paradisiaca), lemon (Citrus limonum) and orange (Citrus sinensis) peel were evaluated. In order to perform these experiments, grinded dried cortexes were used as package in 100 mm high, 10 mm i.d. columns. The grinded material was powdered in a mortar and passed through a screen in order to get two different particle sizes, 2 and 1 mm, for all powders. To estimate the biosorption capabilities of the tested materials, different heavy metals were passed through the columns and the elution filtrate reloaded different times to increase the retention of metals. The heavy metals used were prepared as synthetic samples at 10 mg/L of Pb(NO₃)₂, Cd(NO₃)₂, and Cu(NO₃)₂·6H₂O using primary standards. In preliminary experiments using banana cortex, it was found that material with 1 mm of particle size showed higher retention capability (up to12%) than the material with 2 mm of particle size. Considering these results, 1 mm particle size material was used in further experiments with the other waste materials. It was found that for Pb and Cu removal, lemon and orange cortex showed better biosorption capability when compared with banana cortex (up to 15% less for Pb and 48% less for Cu). For Cd, banana cortex showed better biosorption capability 57% (67.2 mg/g of cortex) more than orange (28.8 mg/g of cortex), and 82% more than lemon (12 mg/g of cortex). Reload of the columns with the filtrate after passing through the column improved the removal capability of all the materials tested from 10% to 50% depending on the cortex and metal tested.     

Biosorption of Cd(II), Ni(II) and Pb(II) from Aqueous Solution by Dried Biomass of Aspergillus niger: Application of Response Surface Methodology to the Optimization of Process Parameters

In this study, the biosorption of Cd(II), Ni(II) and Pb(II) on Aspergillus niger in a batch system was investigated, and optimal condition determined by means of central composite design (CCD) under response surface methodology (RSM). Biomass inactivated by heat and pretreated by alkali solution was used in the determination of optimal conditions. The effect of initial solution pH, biomass dose and initial ion concentration on the removal efficiency of metal ions by A. niger was optimized using a design of experiment (DOE) method. Experimental results indicated that the optimal conditions for biosorption were 5.22 g/L, 89.93 mg/L and 6.01 for biomass dose, initial ion concentration and solution pH, respectively. Enhancement of metal biosorption capacity of the dried biomass by pretreatment with sodium hydroxide was observed. Maximal removal efficiencies for Cd(II), Ni(III) and Pb(II) ions of 98, 80 and 99% were achieved, respectively. The biosorption capacity of A. niger biomass obtained for Cd(II), Ni(II) and Pb(II) ions was 2.2, 1.6 and 4.7 mg/g, respectively. According to these observations the fungal biomass of A. niger is a suitable biosorbent for the removal of heavy metals from aqueous solutions. Multiple response optimization was applied to the experimental data to discover the optimal conditions for a set of responses, simultaneously, by using a desirability function.     

Cercis siliquastrum Tree Leaves as an Efficient Adsorbent for Removal of Ag(I): Response Surface Optimization and Characterization of Biosorption

The Cercis siliquastrum tree leaves are introduced as a low cost biosorbent for removal of Ag(I) from aqueous solution in a batch system. FT‐IR, XRD analysis, and potentiometric titration illustrate that the adsorption took place and the acidic functional group (carboxyl) of the sorbent was involved in the biosorption process. In addition, it was observed that the pH beyond pH_pzc 4.4 is favorable for the removal procedure. The effect of operating variables such as initial pH, temperature, initial metal ion concentration, and sorbent mass on the Ag(I) biosorption was analyzed using response surface methodology (RSM). The proposed quadratic model resulting from the central composite design approach (CCD) fitted very well to the experimental data. The optimum condition obtained with RSM was an initial concentration of Ag(I) of 85 mg L^?1, pH = 6.3 and sorbent mass 0.19 g. The applicability of different kinetic and isotherm models for current biosorption process was evaluated. The isotherm, kinetic, and thermodynamic studies showed the details of sorbate‐sorbent behavior. The competitive effect of alkaline and alkaline earth metal ions during the loading of Ag(I) was also considered.     

Biosorption of heavy metals by a marine bacterium

Heavy metal chelation property of exopolysaccharide produced by Enterobacter cloaceae, a marine bacterium, isolated from the West Coast of India, is reported in this paper. The exopolysaccharide demonstrated excellent chelating properties with respect to cadmium (65%) followed by copper (20%) and cobalt (8%) at 100 mg/l heavy metal concentration. However, it could not chelate mercury. A comparative study of the percentage biosorption of the above mentioned metals is presented here.     

Biosorption Kinetics and Isotherm Studies of Cd(II) by Dried Enteromorpha compressa Macroalgae Cells from Aqueous Solutions

For the first time ever, Enteromorpha compressa macroalgae (ECM), which is commonly found in Turkey, has been used as biosorbent by us. This study aims to investigate the biosorption of Cd²⁺ from aqueous solutions in a batch system by using an alga of ECM in different concentrations, pH levels, agitation rates (90–150 rpm), and contact periods. The maximum biosorption capacity of the ECM was found to be 9.50 mg/g at pH 6, Cd²⁺ initial concentration of 10 mg/L and agitation rate 150 rpm. Cadmium removal efficiency was about 95%. The experimental isotherm data were analyzed using the Langmuir and Freundlich equations. Isotherm parameters for both equations were determined and discussed. The stated biosorption mechanism is explained by the Freundlich isotherm (r² = 0.998) theory. Two simplified kinetic models including a pseudo‐first‐ and second‐order equation were selected to follow the biosorption process. Kinetic parameters; rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the biosorption of cadmium onto ECM could be described by the pseudo‐second‐order equation (r² > 0.99).     

Remediation of Radionuclide Pollutants through Biosorption – an Overview

The development of nuclear science and technology has led to the increase of nuclear wastes containing radionuclides to be released and disposed in the environment. Pollution caused by radionuclides is a serious problem throughout the world. To solve the problem, substantial research efforts have been directed worldwide to adopt sustainable technologies for the treatment of radionuclide containing wastes. Biosorption represents a technological innovation as well as a cost effective excellent remediation technology for cleaning up radionuclides from aqueous environment. A variety of biomaterials viz. algae, fungi, bacteria, plant biomass, etc. have been reported for radionuclide remediation with encouraging results. This paper reviews the achievements and current status of radionuclide remediation through biosorption which will provide insights into this research frontier.     

Biosorption of Procion Red MX 5B by Bacillus subtilis and Its Extracellular Polysaccharide: Effect of Immobilization

Bacillus subtilis and its extracellular polysaccharide (EPS) were used in free form as well as immobilized form as biosorbent for the removal of an anionic dye Procion Red MX 5B. Low pH was favourable for biosorption. Immobilization resulted in reduced biosorption of the dye. The presence of functional groups responsible for the high adsorption capacity in free cells (FC) and EPS was confirmed by FTIR analysis. High Q_max and b values were noted in the case of FC and free EPS in contrast to immobilized cells and EPS. The kinetics data showed that the adsorption system followed pseudo‐first‐order reaction at low dye concentration. Desorption of the dye was found to be 100% in 1 N NaOH. In the case of immobilized biomass and EPS the alginate was found to be unstable under high alkaline conditions of NaOH.     

Chromium Removal through Biosorption and Bioaccumulation by Bacteria from Tannery Effluents Contaminated Soil

Four bacterial isolates (two resistant and two sensitive to chromium) were isolated from soil contaminated with tannery effluents at Jajmau (Kanpur), India, and were identified by 16S rDNA gene sequencing as Stenotrophomonas maltophilia, Exiguobacterium sp., Pantoea sp., and Aeromonas sp. Biosorption of chromium by dried and living biomasses was determined in the resistant and sensitive isolates. The effect of pH, initial metal concentration, and contact time on biosorption was studied. At pH 2.5 the living biomass of chromium resistant isolate Exiguobacterium sp. ZM‐2 biosorbed maximum amount of Cr⁶⁺ (29.8 mg/g) whereas the dried biomass of this isolate biosorbed 20.1 mg/g at an initial concentration of 100 mg/L. In case of chromate sensitive isolates, much difference was not observed in biosorption capacities between their dried and living biomasses. The maximum biosorption of Cr³⁺ was observed at pH 4.5. However, biosorption was identical in resistant and sensitive isolates. The data on chromium biosorption were analyzed using Langmuir and Freundlich isotherm model. The biosorption data of Cr⁶⁺ and Cr³⁺ from aqueous solution were better fitted in Langmuir isotherm model compared to Freundlich isotherm model. Metal recovery through desorption was observed better with dried biomasses compared to the living biomasses for both types of chromium ions. Bioaccumulation of chromate was found higher in chromate resistant isolates compared to the chromate sensitive isolates. Transmission electron microscopy confirmed the accumulation of chromium in cytoplasm in the resistant isolates.     

Experimental and Isothermal Studies on Sorption of Congo Red by Modified Mycelial Biomass of Wood‐rotting Fungus

Batch biosorption experiments were carried out for the removal of Congo red from aqueous solution using native and pretreated mycelial pellets/biomass of Trametes versicolor. The effect of process parameters such as contact time, dye concentration, and pH on the extent of Congo red biosorption has been investigated. Higher dye concentrations resulted in lower biosorption. Increases in biomass dosage led to increases in the levels of biosorption. Biosorption kinetics and equilibrium data are essential basic requirements to develop an effective and accurate design model for the removal of the dye. A kinetic study showed that the biosorption of the dye on fungal biomass was a gradual process. Pseudo‐first‐order, pseudo‐second‐order, and Bangham's model were used to fit the experimental data. The results of the kinetic studies showed that the second‐order kinetic model fitted well for the present experimental data. Equilibrium isotherms were analyzed by Langmuir, Freundlich, Dubnin‐Radushkevich, and Temkin isotherms. The biosorption equilibrium data obeyed the Langmuir and Temkin isotherms well. Acidic pH was favorable for the biosorption of the dye. Studies on the pH effect and desorption show that chemisorption seems to play a major role in the biosorption process. Among the native and pretreated biomass studied, autoclaved biomass showed a better biosorption capacity.     

Assessment of the Biosorption Characteristics of a Spent Cottonseed Husk Substrate for the Decolorization of Methylene Blue

This study concentrates on the possible application of the spent cottonseed husk substrate (SCHS), an agricultural waste used after the cultivation of white rot fungus Flammulina velutipes, to adsorb methylene blue (MB) from aqueous solutions. Batch studies were carried out with variable initial solution pH, adsorbent amount, reaction time, temperature, and initial MB concentration. MB uptake was favorable at pH ranging from 4.0 to 12.0, and the equilibrium adsorption capacity of 143.5 mg g^?1 can be reached promptly within about 240 min. The combination analysis of FTIR and BET techniques revealed that the massive functional groups on the biosorbent surface, such as hydroxyl and carboxyl, were responsible for the biosorption of MB. It was found that adsorption data matched the pseudo‐second order kinetic and Langmuir isotherm models. Thermodynamic parameters of free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°), obtained from biosorption MB ranging from 293 to 313 K, showed that the sorption experiment was a spontaneous and endothermic process. The study highlighted a new pathway to develop a new potential utilization of SCHS as a low‐cost sorbent for the removal of MB pollutants from wastewater.     

Application of Agro‐Based Biomasses for Zinc Removal from Wastewater – A Review

Zinc remediation of aqueous streams is of special concern due to its highly toxic and persistent nature. Conventional treatment technologies for the removal of zinc are not economical and further generate huge quantity of toxic chemical sludge. Biosorption is emerging as a potential alternative to the existing conventional technologies for the removal of metal ions from aqueous solutions. Mechanisms involved in the biosorption process include chemisorption, complexation, adsorption–complexation on surface and pores, ion exchange, microprecipitation, heavy metal hydroxide condensation onto the bio surface, and surface adsorption. Biosorption largely depends on parameters such as pH, the initial metal ion concentration, biomass concentration, presence of various competitive metal ions in solution, and to a limited extent on temperature. Biosorption using biomass such as agricultural wastes, industrial residues, municipal solid waste, biosolids, food processing waste, aquatic plants, animal wastes, etc., is regarded as a cost‐effective technique for the treatment of high volume and low concentration complex wastewaters containing zinc metal. Very few reviews are available where readers can get an overview of the sorption capacities of agro based biomasses used for zinc remediation together with the traditional remediation methods. The purpose of this review article is to provide the scattered available information on various aspects of utilization of the agro based biomasses for zinc metal ions removal. An extensive table summarizes the sorption capacities of various adsorbents. These biosorbents can be modified using various methods for better efficiency and multiple reuses to enhance their applicability at industrial scale. We have incorporated most of the valuable available literature on zinc removal from waste water using agro based biomasses in this review.     

Cd(II), Pb(II) and Zn(II) Removal from Contaminated Water by Biosorption Using Activated Sludge Biomass

Biosorption using activated sludge biomass (ASB) as a potentially sustainable technology for the treatment of wastewater containing different metal ions (Cd(II), Pb(II) and Zn(II)) was investigated. ASB metal uptake clearly competed with protons consumed by microbial biomass compared with control tests with non‐activated sludge biomass. Biosorption tests confirmed maximum exchange between metal ions and protons at pH 2.0–4.5. It was revealed by the study that the amount of metal ions released from the biomass increased with biomass sludge concentration. The result showed that maximum absorption of metal ions was observed for Cd(II) at pH 3.5, Pb(II) at pH 4.0, and pH 4.5 for Zn(II) ions. The maximum absorption capacities of ASB for Cd(II), Pb(II) and Zn(II) were determined to be 59.3, 68.5 and 86.5%, respectively. The biosorption of heavy metals was directly proportional to ASB stabilization corresponding to a reduction in heavy metals in the order of Cd < Pb < Zn. The order of increase of biosorption of metal ions in ASB was Zn(II) < Pb(II) < Cd(II), and this was opposite to that of non active sludge. The results indicate that ASB is a sustainable tools for the bioremediation of Cd(II), Pb(II) and Zn(II) ions from industrial sludge and wastewater treatment plants.     

Dynamic,Mechanistic, and Thermodynamic Modeling of Zn(II) Ion Biosorption onto Zinc Sequestering Bacterium VMSDCM

The surface of the bacterial cells before the biosorption of Zn(II) ion has been found rough, heterogeneous, and non‐crystalline together with tremendous protrusions and negatively charged functional groups. The bacterium was characterized as rod shaped with Gram‐negative type of cell wall structure. In reaction dynamics, pseudo‐second‐order kinetics with higher linear correlation coefficient (R²) ranging between 0.97 and 0.99, lower sum of square errors (SSE) (0.035–0.081) and chi (χ²) (0.0013–0.009) provided a better explanation of sorption of Zn(II) ion on bacterium surface as compared to pseudo‐first‐order model. The removal of Zn(II) was governed by both film and intra‐particle diffusion at onset and later stage of sorption of metal ion on the surface of bacterial cells. The R² (0.92–0.94) for intra‐particle diffusion model was quite higher with lower values of SSE (9.56–16.33) and chi (χ²) (11.26–19.65) against the Bangham's model. The positive value of ΔH (16.628 × 10^?6 kJ/mol) and ΔS (5320.90 kJ/mol/K) showed that the biosorption of Zn(II) ion across liquid phase on bacterial surface was endothermic with increased randomness at solid–liquid interface. The negative values of ΔG demarcated the whole process as spontaneous in nature. In the present work, the distribution coefficient was found to be > 0.5 at various temperature ranges. At the attainment of equilibrium, the residual concentration of Zn(II) ion in liquid phase was around 0.6 mg/L, which was much below the limit described by United States Environmental Protection Agency (USEPA), i.e. 5 mg/L.     

Equilibrium,Thermodynamic, and Kinetic Studies on Lead (II) Biosorption from Aqueous Solution by Saccharomyces cerevisiae Biomass

This paper presents a biosorption procedure for the preconcentration of Pb²⁺ ions using Saccharomyces cerevisiae biomass. The influence of several factors including pH, biomass dosage, contact time, and temperature on biosorption efficiency were optimized. At optimum value of all the equilibrium, thermodynamic, and kinetic parameters of Pb²⁺ ion biosorption was investigated by testing the Langmuir and Freundlich models and first and second order kinetic models were applied. The biosorption capacity of S. cerevisiae biomass was determined 89.6 mg/g, while the retained Pb²⁺ ions by S. cerevisiae were reversibly eluted using 5 mol/L HNO₃. Due to the high stability of S. cerevisiae the applied biomass can be used successively ten times with a slightly decrease (about 20%) in the recovery of Pb²⁺ ions. The calculated thermodynamic parameters, ΔG°, ΔH°, and ΔS° showed that the biosorption of Pb²⁺ ion onto S. cerevisiae biomass was feasible, spontaneous, and endothermic under examined conditions. The results of kinetic analysis showed that the biosorption processes of Pb²⁺ ions onto S. cerevisiae biomass followed pseudo second order kinetics.     

Pesticides Removal Using Conventional and Low‐Cost Adsorbents: A Review

Worldwide pesticide usage has increased dramatically during the last three decades, coinciding with changing practices and increasing by intensive agriculture. This widespread use of pesticides for agricultural and non‐agricultural purposes has resulted in the presence of their residues in various environmental matrices. The occurrence of pesticides and their metabolite transported in rivers, channels, lakes, sea, air, soils, groundwater, and even drinking water, proves the high risk of these chemicals to human health and the environment. Therefore, pesticide removal is of an increasing concern. In this study, a review of the published literature dealing with pesticides removal process is presented. Firstly, pesticide removal by conventional means is briefly considered. Secondly, the use of the low‐cost sorbent through biosorption process is discussed comprehensively. The effect of factors such as pH, contact time, sorbent dosage, initial pesticide concentration, and optimization of biosorption conditions is also discussed. Kinetic, thermodynamic, and mechanism studies are also given. This study shows that both microorganisms and other materials with biological origin like agricultural by‐products may be used to this end. There is a significant potential for pesticide uptake by the use of various pristine and especially modified biosorbents. In the case of living organisms used as removal agents, degradation may also play a role in the total removal observed.     

Oreganum Stalks as a New Biosorbent to Remove Textile Dyes from Aqueous Solutions

In the present study, Oreganum onites L. stalks in natural and chemically modified with HNO³ and H³PO⁴ used as adsorbent for removal of both acidic and basic dyes from waters. The adsorption was studied as a function of pH and contact time by batch method. All tested biosorbents were characterized by FT‐IR, scanning electron microscopy, and measuring the pH dependence of the zeta potential. The adsorption isotherms were fitted to Langmuir isotherm. The maximum adsorption capacity of dyes was 280.73 mg g^?1 for Basic Red 18, 147.06 mg g^?1 for methylene blue and 112.36 for Acid Red 111, which is comparable to that of other lignocellulosic materials. The modification process was considerably increased the biosorption capacity of lignocellulosic material, resulting in a 56–63% increase in the biosorption capacity of basic dyes and a 125% increase in the biosorption capacity of acidic dye. The present study illustrated that the most effective factors in the adsorption of basic dye were surface charge and acidic groups on lignocellulosic biosorbents, while non‐electrostatic forces as well as electrostatic forces were also effective in the adsorption of acidic dye. In conclusion, Oreganum stalks can be considered as a very prospective adsorbent for the removal of tested basic and acidic dyes.     

Zn(II) Ion Biosorption onto Surface of Eucalyptus Leaf Biomass: Isotherm,Kinetic, and Mechanistic Modeling

Bioremediation of Zn(II) by biosorption across aqueous phase on to surface of eucalyptus leaf powder has been investigated in present research work. The adsorptive potential of eucalyptus leaf powder was evaluated as function of pH, temperature, contact time, agitation rate and particle size. Maximum metal ion uptake and percentage removal capacity of eucalyptus leaf powder were 23.5 mg g⁻¹ and 94%, respectively, at optimized pH 5, 20 ± 1°C, contact time 6 h, particle size 0.5 mm and agitation rate 200 rpm. The biomass surface analysis revealed the fact that the biomass surface was heterogeneous and porous in nature. The functional groups like amine, amide, carboxyl, hydroxyl, and methyl groups, significantly important for metal ion binding were present on biomass surface in tremendous amount. Additionally, the Fourier transformation IR spectrum analysis of acid and base activated eucalyptus leaf biomass ruled out all the possibilities of the presence of surface functional groups mentioned above. The reaction rate was studied by applying two rate limiting models pseudo first and pseudo second order. Pseudo second order model was found to be more suitable (R² = 0.998) in comparison to pseudo first order (R² = 0.724). Adsorption equilibrium of batch stirred reaction data fitting shows the dominance of Langmuir isotherm (R² = 0.99) against Freundlich isotherm (R² = 0.887) model with equipartitional involvement of both film and intra particle diffusion as rate limiting steps at differential status of contact time.     

Biosorption of Methylene Blue from Aqueous Solution Using a Bioenergy Forest Waste: Xanthoceras sorbifolia Seed Coat

Xanthoceras sorbifolia seed coat (XSSC), a bioenergy forest waste, was used for the adsorption of methylene blue (MB) from aqueous solutions. The effects of adsorbent dosage, pH, adsorbate concentration and contact time on MB biosorption were studied. The equilibrium adsorption data was analyzed by Langmuir and Freundlich isotherm models. The results indicated that the Langmuir model provided the best correlation with the experimental data. The adsorption capacity of XSSC for MB was determined with the Langmuir model and was found to be 178.6 mg/g at 298 K. The adsorption kinetic data was modeled using the pseudo‐first order, pseudo‐second order, and intraparticle diffusion kinetic equations. It was seen that the pseudo‐second order equation could describe the adsorption kinetics, and intraparticle diffusion was not the sole rate controlling factor. Thermodynamic parameters were also evaluated. Standard Gibbs free energy was spontaneous for all interactions, and the biosorption process exhibited exothermic standard enthalpy values. The results indicated that XSSC is an attractive alternative for removing cationic dyes from wastewater.