Response Surface Modeling of Cu(II) Removal from Electroplating Waste by Adsorption: Application of Box–Behnken Experimental Design

The use of kaolinite‐based clay minerals as a low‐cost natural adsorbent for the removal of Cu(II) from electroplating waste leachate was studied. Batch experiments were conducted to determine the effects of varying adsorbent loading, initial pH, adsorbent dosage, and contact time. Box–Behnken design with three variables like initial pH, adsorbent dosage, and contact time at three different levels was studied to identify a significant correlation between the effects of these variables to the amount of Cu(II) adsorbed. The methodology identifies the principal experimental variables, which have the greatest effect on the adsorption process. After optimizing the input variables by using Simplex algorithm, the adsorption of Cu(II) was maximal (99.9% with a maximum (positive) standard deviation of 9.4) at pH 6.24, adsorbent dosage of 0.83 g L^?1, and contact time of 97 min, respectively. Furthermore, the experimental values are in good agreement with predicted values, the correlation coefficient and adjusted correlation coefficients were found to be 0.96 and 0.87, respectively.     

Adsorption of Metal Ions onto the Chemically Modified Agricultural Waste

This paper discusses about the adsorption of metal ions such as Cu(II), Cd(II), Zn(II), and Ni(II) from aqueous solution by sulfuric acid treated cashew nut shell (STCNS). The adsorption process depends on the solution pH, adsorbent dose, contact time, initial metal ions concentration, and temperature. The adsorption kinetics was relatively fast and equilibrium was reached at 30 min. The adsorption equilibrium follows Langmuir adsorption isotherm model. The maximum adsorption capacity values of the modified cashew nut shell (CNS) for metal ions were 406.6 mg/g for Cu(II), 436.7 mg/g for Cd(II), 455.7 mg/g for Zn(II), and 456.3 mg/g for Ni(II). The thermodynamic study shows the adsorption of metal ions onto the STCNS was spontaneous and exothermic in nature. The kinetics of metal ions adsorption onto the STCNS followed a pseudo‐second‐order kinetic model. The external mass transfer controlled metal ions removal at the earlier stages and intraparticle diffusion at the later stages of adsorption. A Boyd kinetic plot confirms that the external mass transfer was the slowest step involved in the adsorption of metal ions onto the STCNS. A single‐stage batch adsorber was designed using the Langmuir adsorption isotherm equation.     

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.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

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.     

A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Use of Pistachio Shells as an Adsorbent for the Removal of Zinc(II) Ion

In this study, the removal of zinc(II) ion from an aqueous solution by pistachio shells (PS) is investigated. The dynamic behavior of the adsorption is examined on the effects of pH, adsorbent dosage, and contact time. The adsorption rates are determined quantitatively and simulated by the Lagergren first order, pseudo‐second order, Elovich, and intra‐particle diffusion kinetic models. The adsorption kinetic models are also tested for validity. The thermodynamic parameters, which are also deduced from adsorption experiments, are very useful in elucidating the nature of adsorption. The experimental results reveal that the optimum pH value and the contact time for the adsorption of Zn²⁺ onto PS are found as 6 and 10 min, respectively. According to these parameters, adsorption process follows the pseudo‐second order kinetic model with high correlation coefficients (R² = 0.999). The obtained results demonstrate that PS is a reasonably effective adsorbent for the removal of Zn²⁺ from aqueous leachate of hazardous waste.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Investigation of the Possibility of Copper Removal from Industrial Leachate by Raw and Calcined Phosphogypsum: D‐Optimal and Taguchi Designs

In the present study, the removal of Cu(II) was evaluated by raw and calcined phosphogypsum (PG) as an industrial product. The role of experimental factors on the removal of Cu(II) was examined by using D‐optimal and Taguchi designs. The experimental factors and their related levels were selected as initial pH of 3–6–8, adsorbent content of 5, 10, and 25 g L^?1, contact time of 5, 10, and 20 min, and temperature of 20, 40, and 60°C. The results are evaluated by ANOVA test to extract important experimental factors and their levels. The performances of the suggested factorial designs were then compared and regression models that took into account the significant main and interaction effects were suggested. Taguchi design was found as a reliable solution with less number of experiments for adsorption studies with the optimized values. The resultant removal efficiency is calculated as 78.34%. The results revealed that calcined PG is an appropriate adsorbent for Cu(II) removal from leachate of industrial waste.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

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.     

Sorptive Potential of Beach Sand to Remove Ni(II) Ions: An Equilibrium Isotherm Study

The potential to remove Ni(II) ions from aqueous solutions using sea beach sand, a carbonate‐quartz mineral, was thoroughly investigated. The effects of relevant parameters such as solution pH, adsorbent dose, metal ions concentration, and temperature on Ni(II) sorption onto beach sand were examined. The sorption data followed the Langmuir, Freundlich and Dubinin‐Radushkevich (D‐R) isotherms. The adsorption was endothermic in nature at ambient temperature and the computation of the parameters, ΔH, ΔS and ΔG indicated the interactions between sorbate and sorbent to be thermodynamically favorable. Equilibrium was achieved very quickly within 30 min of shaking. A pseudo‐first order Lagergren equation was used to test the adsorption kinetics. Other kinetic models, e. g., the Morris‐Weber and Reichenberg equations, were used to calculate the rate constant of intraparticle diffusion and the fate of the diffusion process, respectively. The influence of some of the common cations and anions were also a subject of this study.     

Malachite Green Removal from Aqueous Solution by the Peel of Cucumis sativa Fruit

This study investigates the potential use of activated carbon prepared from the peel of Cucumis sativa fruit for the removal of malachite green (MG) dye from simulated wastewater. The effects of different system variables, adsorbent dosage, initial dye concentration, pH, and contact time were investigated and optimal experimental conditions were ascertained. The results showed that when the amount of the adsorbent increased, the percentage of dye removal increased accordingly. Optimum pH value for dye adsorption was 6.0. Maximum dye was sequestered within 50 min of the start of every experiment. The adsorption of MG followed the pseudo‐second‐order rate equation and fits the Langmuir, Freundlich, Dubinin–Radushkevich (D–R), and Tempkin equations well. The maximum removal of MG was obtained at pH 6 as 99.86% for adsorbent dose of 1 g/50 mL and 25 mg L^?1 initial dye concentration at room temperature. Activated carbon developed from the peel of C. sativa fruit can be an attractive option for dye removal from diluted industrial effluents since test reaction made on simulated dyeing wastewater showed better removal percentage of MG.     

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.     

Preparation,Characterization and Adsorption Mechanism of Cu(II) onto Protonated Rubber Leaf Powder

The adsorption of Cu(II) onto HCl treated rubber leaf powder (HHBL) was investigated in batch and column studies. The adsorbent was characterized by spectroscopic and quantitative analyses in order to understand the mechanism of copper adsorption. HHBL is mesoporous in nature as indicated by Bruneuer, Emmett and Teller (BET) analysis, and has various kinds of functional groups such as Si‐OH, ROH, RCOOH, RCOO^–, RNH₂, C‐O‐C and aromatic rings as detected by Fourier transform infrared (FTIR) spectroscopy. Copper adsorption was confirmed by scanning electron microscopy (SEM) and energy dispersive X‐ray spectroscopy (EDS). The equilibrium process was described well by the Langmuir isotherm model, and a maximum adsorption capacity of 8.39 mg/g was recorded for the smallest adsorbent size (<180 μm). The two main adsorption mechanisms involved were ion exchange and complexation. The fixed bed column study demonstrated satisfactory applicability of HHBL in removing Cu(II) from aqueous solutions.     

Adsorptive Removal of Acid Blue 15: Equilibrium and Kinetic Study

Activated carbons prepared from sunflower seed hull have been used as adsorbents for the removal of acid blue 15 (AB‐15) from aqueous solution. Batch adsorption techniques were performed to evaluate the influences of various experimental parameters, e. g., temperature, adsorbent dosage, pH, initial dye concentration and contact time on the adsorption process. The optimum conditions for AB‐15 removal were found to be pH = 3, adsorbent dosage = 3 g/L and equilibrium time = 4 h at 30°C. The adsorption of AB‐15 onto the adsorbent was found to increase with increasing dosage. It was found from experimental results that the Langmuir isotherm fits the data better than the Freundlich and Temkin isotherms. The maximum adsorption capacity, Q_m (at 30°C) was calculated for SF1, SF2, and SF3 as 75, 125 and 110 mg g^–1 of adsorbent, respectively. It was found that the adsorption follows pseudo‐second order kinetics. The thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated. The activated carbons prepared were characterized by FT‐IR, SEM and BET analysis.     

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 Organochlorine Pesticides from Aqueous Solution by Using Neutralized Red Mud

This work describes the potential usability of neutralized red mud for the removal of organochlorine pesticides (OCPs) from aqueous solutions. After examination on the adsorption capability of neutralized red mud for all studied OCPs, the experiments were performed by employing aldrin as a model compound. The effect of several parameters, such as contact time, pH of the solution, initial aldrin concentration, and dosage of the adsorbent was evaluated by batch experiments. The determination of OCPs was carried out using traditional liquid–liquid extraction followed by a GC coupled with µ‐electron capture detector (GC‐µECD). The results showed that adsorption equilibrium time depended upon the initial aldrin concentration and adsorption followed the second‐order kinetic model. Kinetic study also indicated that the film diffusion mechanism was a main rate control mechanism. The removal was explained by considering the electrostatic interactions between metal oxides surface of the neutralized red mud and inductively charged centers (negative charge (d?) of chlorine atoms and positive charge (d+) of π‐cloud aromatic ring) of the aldrin molecules. In comparison to the Langmuir isotherm model, the Freundlich model better represented the adsorption data. The neutralized red mud was also succesfully employed for the removal of OCPs from real water samples, including tap water and surface (lake) water, fortified with studied OCPs.