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).     

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 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.     

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.     

Copper(II) Biosorption on Soda Lignin From Oil Palm Empty Fruit Bunches (EFB)

The adsorption of Cu(II) ions from aqueous solutions by soda lignin as an absorbent using a batch adsorption system is presented in this paper. The soda lignin used in this study was extracted from black liquor derived from oil palm empty fruit bunches (EFB) using 20% v/v sulfuric acid. The effects of varying experimental parameters such as pH value, adsorbent dosage, different concentrations of Cu(II) ions, and agitation period were investigated. The results revealed that the optimum adsorption of Cu(II) onto soda lignin was recorded at a pH of 5.0 at an adsorbent dosage of 0.5 g soda lignin and an agitation period of 40 min. The adsorption capacities and rates of Cu(II) ions onto soda lignin was evaluated. The Langmuir and Freundlich adsorption models were applied to calculate the isotherm constants. It was found that the adsorption isothermal data could be well interpreted by the Freundlich model. The kinetic experimental data properly correlated with the pseudo‐second‐order kinetic model, which implies that chemical sorption is the rate‐limiting step.     

Equilibrium and Kinetic Studies on the Removal of Reactive Red 2 Dye from an Aqueous Solution Using a Positively Charged Functional Group of the Nymphaea rubra Biosorbent

Nymphaea rubra stem was used as a low cost and easily available biosorbent for the removal of Reactive Red 2 dye from an aqueous solution. Initially, the effects of biosorbent dosage (0.2–1.0 g L^–1), pH (1–6), and dye concentration (30–110 mg L^–1) on dye removal were studied. Batch experiments were carried out for biosorption kinetics and isotherm studies. The results showed that dye uptake capacity was found to increase with a decrease in biosorbent dosage. Equilibrium uptake capacity was found to be greatest at a pH value of 2.0, when compared to all other pH values studied. The equilibrium biosorption isotherms were analyzed by the Freundlich and Langmuir models. The equilibrium data was found to fit very well with the Freundlich isotherm model when compared to the Langmuir isotherm model. The kinetic data was analyzed using pseudo-first order and pseudo-second order kinetic models. From the results, it was observed that the kinetic data was found to fit the pseudo-second order kinetic model very well. The surface morphology of the stem of the N. rubra biosorbent was exemplified by scanning electron microscopy. Fourier transform infrared analysis was employed to confirm the existence of an amine group in the stem of N. rubra.     

Removal of Cadmium from Aqueous Solution Using Castor Seed Hull: A Kinetic and Equilibrium Study

The effects of various parameters such as initial concentration, adsorbent loading, pH, and contact time on kinetics and equilibrium of adsorption of Cd²⁺ metal ion from its aqueous solution by castor seed hull (CSH) and also by activated carbon have been investigated by batch adsorption experiments. The amount of adsorption increases with initial metal ion concentration, contact time, solution pH, and the loading of adsorbent for both the systems. Kinetic experiments indicate that adsorption of cadmium metal ion on both CSH and on activated carbon consists of three steps – a rapid adsorption of cadmium metal ion, a transition phase, and an almost flat plateau region. This has also been confirmed by the intraparticle diffusion model. The lumped kinetic results show that the cadmium adsorption process follows a pseudo‐second order rate law. The kinetic parameters including the rate constant are determined at different initial metal ion concentrations, pH, amount, and type of adsorbent, respectively. The Langmuir and Freundlich adsorption isotherm models are used to describe the experimental data. The Langmuir model yields a better correlation coefficient than the other model. A comparison of the monolayer adsorption capacity (q_m) of CSH, activated carbon, and several other reported adsorbents has been provided. The value of separation factor (R_L) calculated from the Langmuir equation also gives an indication of favorable adsorption of the metal ion. From comparative studies, it has been found that CSH is a potentially attractive adsorbent than commercial activated carbon for cadmium metal ion (Cd²⁺) removal.     

Adsorption Kinetic and Equilibrium Studies on Removal of Lead(II) onto Glutamic Acid/Sepiolite

In this study, a modified method was used to increase the adsorption of lead ions from aqueous solutions by using modified clay mineral on the laboratory scale. Adsorption experiments have been carried out on the use of both thermal activated sepiolite (TAS) and their glutamate/sepiolite modification (GS) as adsorbents. The experimental data was analyzed using adsorption kinetic models (pseudo first‐ and second‐order equations). The pseudo second‐order kinetic model fitted well to the kinetic data (R² ≥ 0.99). Then, the Freundlich and Langmuir models were applied to describe the uptake of Pb(II) on GS and the Langmuir isotherm model agrees well with the equilibrium experimental data (R² ≥ 0.97). The maximum adsorption capacity was observed to be 128.205 mg/g by GS according to the Langmuir equation. Desorption efficiency of the GS was studied by the batch method using EDTA, HCl, and HNO₃ solutions. Desorption of 69.18, 74.55, and 80% of Pb(II) from GS was achieved with 0.1 M EDTA, 0.1 M HCl, and 0.1 M HNO₃ solutions, respectively. FTIR analysis suggests the importance of functional groups such as amino, hydroxyl, and carboxyl during Pb(II) removal. SEM observations demonstrated that an important interaction at the lead‐modified sepiolite interface occurred during the adsorption process. In addition, the thermodynamic constants was calculated that the values of the Gibbs free energy (ΔG*), enthalpy (ΔH*), and entropy (ΔS*) of modification were 86.79 kJ/mol, ?18.91 kJ/mol, and ?354.70 J/mol/K, respectively. The negative value of ΔH* shows exothermic nature of adsorption.     

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.     

Removal and Recovery of Molybdenum from Aqueous Solutions by Adsorption onto Surfactant‐Modified Coir Pith,a Lignocellulosic Polymer

Coconut coir pith, a lignocellulosic polymer, is an unwanted by‐product of the coir fiber industry. The pith was used as a biosorbent for the removal of Molybdenum(VI) after modification with a cationic surfactant, hexadecyltrimethylammonium bromide. The optimum pH for maximum adsorption of Mo(VI) was found to be 3.0. Langmuir, Freundlich and Dubinin Radushkevich isotherms were used to model the adsorption equilibrium data and the system was seen to follow all three isotherms. The Langmuir adsorption capacity of the biosorbent was found to be 57.5 mg g^–1. Kinetic studies showed that the adsorption generally obeyed a second‐order kinetic model. Desorption studies showed that the recovery of Mo(VI) from the spent adsorbent was feasible. The effect of foreign anions on the adsorption of Mo(VI) was also examined.     

Recent Progress on Biosorption of Heavy Metals from Liquids Using Low Cost Biosorbents: Characterization,Biosorption Parameters and Mechanism Studies

A significant number of biosorption studies on the removal of heavy metal from aqueous solutions have been conducted worldwide. Nearly all of them have been directed towards optimizing biosorption parameters to obtain the highest removal efficiency while the rest of them are concerned with the biosorption mechanism. Combinations of FTIR, SEM‐EDX, TEM as well as classical methods such as titrations are extremely useful in determining the main processes on the surfaces of biosorbents. Diverse functional groups represented by carboxyl, hydroxyl, sulfate and amino groups play significant roles in the biosorption process. Solution pH normally has a large impact on biosorption performance. In brief, ion exchange and complexation can be pointed out as the most prevalent mechanisms for the biosorption of most heavy metals.     

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.     

Adsorption of Chromium(III), Nickel(II), and Copper(II) from Aqueous Solution by Activated Alumina

The possible use of activated alumina powder (AAP) as adsorbent for Cr(III), Ni(II), and Cu(II) from synthetic solutions was investigated. The effect of various parameters on batch adsorption process such as pH, contact time, adsorbent dosage, particle size, temperature, and initial metal ions concentration were studied to optimize the conditions for maximum metal ion removal. Both higher (molar) and lower (ppm) initial metal ion concentration sets were subjected to adsorption on AAP. Adsorption process revealed that equilibrium was established in 50 min for Cr(III) at pH 4.70, 80 min for Ni(II) at pH 7.00, and 40 min for Cu(II) at pH 3.02. Percentage removal was found to be highest at 55°C for Cr(III) and Ni(II) with 420 µm and 45°C for Cu(II) with 250‐µm particle size AAP. A dosage of 2 g for Cr(III), 8 g for Ni(II), and 10 g Cu(II) gave promising data in the metal ion removal. The adsorption process followed Langmuir as well as Freundlich models. The thermodynamics of adsorption of these metal ions on activated aluminum indicated that the adsorption was spontaneous and endothermic in nature. Present study indicates that AAP can act as a promising adsorbent for industrial wastewater treatment.     

Equilibrium,Kinetic, and Thermodynamic Studies on the Adsorption of Triclosan onto Multi‐Walled Carbon Nanotubes

The increased accumulation of toxic pharmaceuticals and personal care products in the environment is a concern of worldwide relevance. Efficient technologies are needed to mitigate the level of such chemicals in natural waters. The suitability of multi‐walled carbon nanotubes (MWCNTs) to remove aqueous triclosan (a widely used anti‐microbial agent) was investigated in the present study. Tested operational parameters included the pH (3.0–11.0) value and the ionic strength (10^?3, 10^?2, and 10^?1 M). Kinetic and thermodynamic studies were conducted at different initial concentrations (4, 8, and 10 mg/L) and temperatures (288, 298, and 308 K). Results showed higher triclosan adsorption at pH 3.0 (157.7 mg/g) than at pH 11.0 (103.9 mg/g). With an increase of ionic strength from 10^?3 to 10^?2 M, the adsorption capacity increased from 136.1 to 153.1 mg/g and from 80.8 to 105.8 mg/g at pH 3.0 and 10.0, respectively, while further increase of ionic strength to 10^?1 M slightly reduced the triclosan adsorption to 149.9 and 94.7 mg/g due to the aggregation of MWCNTs. The Polanyi–Manes model (PMM) provided a best fitting of adsorption isotherms to the experimental data, and the kinetic process was well described by the pseudo second‐order kinetic model. The calculated thermodynamic parameters (ΔH⁰ = ?88.08 kJ/mol, ΔS⁰ = ?173.38 J/mol K) suggested that the adsorption of triclosan is spontaneous and exothermic in nature. The findings of the present work have significant implications for the removal of triclosan from aqueous solution with MWCNTs.     

Adsorption of Pb(II) Ions from Aqueous Solutions by Date Bead Carbon Activated with ZnCl2

This study reports on the adsorption characteristics of Pb(II) ions from aqueous solutions using ZnCl₂‐activated date (Phoenix dactylifera) bead (ADB) carbon with respect to change in adsorbent dosage, initial pH, contact time, initial concentration, and temperature of the solution. Kinetic studies of the data showed that the adsorption follows the pseudo‐second‐order kinetic model. Thermodynamic parameters, enthalpy change (ΔH° = 55.11 kJ/mol), entropy change (ΔS° = ? 0.193 kJ/mol/K), and Gibbs free energy change (ΔG°) were also calculated for the uptake of Pb(II) ions. These parameters show that adsorption on the surface of ADB was feasible, spontaneous in nature, and endothermic between temperatures of 298.2 and 318.2 K. The equilibrium data better fitted the Langmuir and Freundlich isotherm models than the D–R adsorption isotherm model for studying the adsorption behavior of Pb(II) onto the ADB carbon. It could be observed that the maximum adsorption capacity of ADB was 76.92 mg/g at 318.2 K and pH 6.5.     

Biosorption of Cadmium(II) Ions by Citrus Peels in a Packed Bed Column: Effect of Process Parameters and Comparison of Different Breakthrough Curve Models

The efficiency of low cost citrus peels as biosorbents for removal of cadmium ions from aqueous solution was investigated in a fixed bed column, a process that could be applied to treat industrial wastewaters similar to commonly used ion exchange columns. Effluent concentration versus time profiles (i.e., breakthrough curves) were experimentally determined in a laboratory‐scale packed bed column for varying operational parameters such as flow rate (2, 9, and 15.5 mL/min), influent cadmium concentration (5, 10, and 15 mg/L), and bed height (24, 48, and 72 cm) at pH 5.5. Column operation was most efficient for empty bed contact times of at least 10 min, which were apparently necessary for mass transfer. While the sorption capacity was largely unaffected by operational variables, the Thomas (Th) rate constant increased with the flow rate, and slightly decreased with increasing column length. Three widely used semi‐mechanistic models (Th, Bohart–Adams, and Yoon–Nelson) were shown to be equivalent and the generalized model was compared with a two‐parameter empirical model (dose‐response). The latter was found to be able to better simulate the breakthrough curve in the region of breakthrough and saturation.     

Base Treated Cogon Grass (Imperata cylindrica) as an Adsorbent for the Removal of Ni(II): Kinetic,Isothermal and Fixed‐bed Column Studies

The adsorption of Ni(II) from aqueous solutions using base treated cogon grass or Imperata cylindrica (NHIC) was performed under batch and column modes. Batch experiments were conducted to determine the factors affecting adsorption such as pH, adsorbent dosage, initial nickel concentration, contact time and temperature. The fixed‐bed column experiment was performed to determine the practical applicability of NHIC and to obtain the breakthrough curve. Adsorption was fast as equilibrium was achieved within 60 min, and was best described by the pseudo second order model. According to the Langmuir model, a maximum adsorption capacity of 6.96 mg/g was observed at pH 5 and at a temperature of 313 K. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated, and indicated that adsorption was a spontaneous and endothermic process. The mechanistic pathway of Ni(II) uptake was examined by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) spectroscopy. The Thomas and Yoon‐Nelson models were used to analyze the fixed‐bed column data.     

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.