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.     

Removal of Chromium from Synthetic Effluent using Nymphaea rubra

In the present work, biosorption of Cr(VI) by Nymphaea rubra was investigated in batch studies. Batch experiments were conducted to study the effect of initial sorbent dosage, solution pH and initial Cr(VI) concentration. The results showed that the equilibrium uptake capacity was increased with decrease in biomass dosage. The Cr(VI) removal was influenced by the initial chromium compound concentration. Langmuir and Freundlich adsorption isotherm models were used to represent the equilibrium data. The Freundlich isotherm model was fitted very well with the equilibrium data when compared to Langmuir isotherm model. The sorption results were analyzed for pseudo‐first order and pseudo‐second order kinetic model. It was observed that the kinetic data fitted very well with the pseudo‐second order rate equation when compared to the pseudo‐first order rate equation. Fourier transform infrared spectrum showed the presence of different functional groups in the biomass. The surface morphology of the sorbent was exemplified by SEM analysis. Aquatic weeds seem to be a promising biosorbent for the removal of chromium ions from water environment. This paper reports the research findings of a laboratory‐based study on the removal of Cr(VI) from the synthetic solution using the dried stem of N. rubra as a biosorbent.     

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.     

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.     

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.     

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.     

Competitive Adsorption of Nickel and Copper Ions from Aqueous Solution Using Nonliving Biomass of the Marine Brown Alga Laminaria japonica

The adsorption of nickel and copper in a bicomponent system using the nonliving biomass of the marine brown alga Laminaria japonica was investigated in batch systems as a function of initial solution pH, contact time and temperature. The adsorption of nickel and copper was strongly pH dependent. Kinetic studies pointed to a rapid uptake with an equilibrium time of about 30 min. The kinetic curves were successfully fitted by linear regression to pseudo first and pseudo‐second‐order equations. The equilibrium data was analyzed using several models, including the extended Langmuir equation, modified extended Langmuir model and combined extended Langmuir‐Freundlich model. The results suggested that the competitive adsorption of nickel and copper at all temperatures was best represented by the combined extended Langmuir‐Freundlich isotherm. The isotherms indicated competitive uptake, with copper being preferentially adsorbed followed by nickel with an increase in the amount of solute in solution. Thermodynamic analysis revealed that the simultaneous adsorption of nickel and copper ions could be considered to be a spontaneous, endothermic process, with increased randomness.     

Removal of Arsenic from Simulated Groundwater Using GAC‐Ca in Batch Reactor: Kinetics and Equilibrium Studies

This paper deals with kinetics and equilibrium studies on the adsorption of arsenic species from simulated groundwater containing arsenic (As(III)/As(V), 1:1), Fe, and Mn in concentrations of 0.188, 2.8, and 0.6 mg/L, respectively, by Ca²⁺ impregnated granular activated charcoal (GAC‐Ca). Effects of agitation period and initial arsenic concentration on the removal of arsenic species have also been described. Although, most of the arsenic species are adsorbed within 10 h of agitation, equilibrium reaches after ～24 h. Amongst various kinetic models investigated, the pseudo second order model is more adequate to explain the adsorption kinetics and film diffusion is found to be the rate controlling step for the adsorption of arsenic species on GAC‐Ca. Freundlich isotherm is adequate to explain the adsorption equilibrium. However, empirical polynomial isotherm gives more accurate prediction on equilibrium specific uptakes of arsenic species. Maximum specific uptake (q_max) for the adsorption of As(T) as obtained from Langmuir isotherm is 135 µg/g.     

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.     

Adsorption Kinetic Modeling of Safranin onto Rice Husk Biomatrix Using Pseudo‐first‐ and Pseudo‐second‐order Kinetic Models: Comparison of Linear and Non‐linear Methods

Batch kinetic studies were carried out for the removal of safranin from aqueous solution using a biomatrix prepared from rice husk. The adsorption kinetic data were modeled using the pseudo‐first‐order and pseudo‐second‐order kinetic equations. The linear and non‐linear forms of these two widely used kinetic models were compared in this study. In order to determine the best‐fitting equation, the coefficient of determination (r²), the sum of the squares of the errors (SSE), sum of the absolute errors (SAE), average relative error (ARE), hybrid fractional error function (HYBRID), Marquardt's percent standard deviation (MPSD), and the Chi‐squared test (χ²) were used as error analysis methods. Results showed that the non‐linear forms of pseudo‐first‐order and pseudo‐second‐order models were more suitable than the linear forms for fitting the experimental data. Non‐linear method is thus more appropriate for estimating the kinetic parameters and should primarily be used to describe adsorption kinetics.     

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.     

Adsorption Characteristics of Reactive Black 5 from Aqueous Solution onto Chitosan

Adsorption of reactive black 5 (RB5) from aqueous solution onto chitosan was investigated in a batch system. The effects of solution pH, initial dye concentration, and temperature were studied. Adsorption data obtained from different batch experiments were modeled using both pseudo first‐ and second‐order kinetic equations. The equilibrium adsorption data were fitted to the Freundlich, Tempkin, and Langmuir isotherms over a dye concentration range of 45–100 µmol/L. The best results were achieved with the pseudo second‐order kinetic and Langmuir isotherm equilibrium models, respectively. The equilibrium adsorption capacity (q_e) was increased with increasing the initial dye concentration and solution temperature, and decreasing solution pH. The chitosan flakes for the adsorption of the dye was regenerated efficiently through the alkaline solution and was then reused for dye removal. The activation energy (E_a) of sorption kinetics was estimated to be 13.88 kJ/mol. Thermodynamic parameters such as changes in free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) were evaluated by applying the van't Hoff equation. The thermodynamics of reactive dye adsorption by chitosan indicates its spontaneous and endothermic nature.     

Adsorption of Two Taste and Odor Compounds IPMP and IBMP by Granular Activated Carbon in Water

Granular activated carbon (GAC) adsorption of two representative taste and odor (T & O) compounds, 2‐isopropyl‐3‐methoxy pyrazine (IPMP), and 2‐isobutyl‐3‐methoxy pyrazine (IBMP), in drinking water was investigated. Results show that the modified Freundlich equation best fit the experimental data during the adsorption isotherm tests, and the pseudo first‐order kinetics and intra‐particle diffusion kinetics well described the adsorption kinetics pattern. The calculated thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) indicated a spontaneous and endothermic adsorption process. Factors affecting the treatment efficiency were carefully evaluated. Acidic and alkaline conditions both favored GAC adsorption of IPMP and IBMP, especially the former. With the GAC dosage increasing, the first order adsorption rates increased, while the intra‐particle adsorption rates decreased. Within 12 h, 200 mg/L GAC could remove >90% of 150 µg/L IPMP and IBMP via adsorption at pH 3–11. Therefore, GAC is a promising treatment technology to control the T & O compounds associated water pollution.     

Adsorption Performance and Mechanism in Binding of Azo Dye by Raw Bentonite

The adsorption behavior of methyl orange (MO) from aqueous solution onto raw bentonite (RB) sample was investigated as a function of parameters such as pH, inorganic anion, contact time, and temperature. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. Langmuir adsorption capacity was found to be 34.34 mg/g at pH 4.0. The pseudo‐first‐order, pseudo‐second‐order kinetic, and the intra‐particle diffusion models were used to describe the kinetic data. The values of the energy (E_a), enthalpy (ΔH^≠), and entropy of activation (ΔS^≠) were calculated as 38.62 kJ/mol, 36.04 kJ/mol, and ?150.05 J/mol K, respectively, at pH 4.0.     

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.     

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.     

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.     

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.     

Adsorption of Phosphate by Biomass Char Deriving from Fast Pyrolysis of Biomass Waste

Biomass char (BC) deriving from fast pyrolysis of biomass was a potential adsorption material due to its relative high fixed‐carbon content and the inherent porous structures. Adsorption of phosphate from aqueous solution by BC was investigated in this paper. The results showed that the adsorption capacity of BC was dependent on pyrolysis conditions, such as temperature and holding time. The maximum adsorption capacity for phosphate was approximately 15.11 mg g^?1 at 298 K. The pseudo‐second order model of the adsorption kinetics indicated that the adsorption process was complex and several mechanisms were involved. Equilibrium isotherm was satisfactorily followed the Freundlich isotherm model. The K_F value in Freundlich equation gradually increased with elevating temperature. Moreover, the thermodynamic constants: ΔG⁰, ΔH⁰, and ΔS⁰ were evaluated as ?6.49 kJ mol^?1 (at 298 K), 13.41 kJ mol^?1, and 66.70 J mol^?1 K^?1, respectively. Phosphate adsorption onto BC was spontaneous and endothermic. As a waste, BC was a potentially attractive adsorbent for phosphate removal from aqueous solution with low cost and high capability.