Cr(VI) Immobilization Process in a Cr‐Spiked Soil by Zerovalent Iron Nanoparticles: Optimization Using Response Surface Methodology

The response surface methodology involving the five‐level central composite design (CCD) was employed to model and optimize the Cr(VI) immobilization process in a Cr‐spiked soil using starch‐stabilized zerovalent iron nanoparticles (ZVIn). ZVIn were synthesized via a borohydride reduction method and characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). All Cr(VI) immobilization experiments were conducted in a batch system. The variables for the CCD optimization were the ZVIn dosage (% w/w), reaction time (min), and initial Cr(VI) concentration in soil (mg/kg). The predicted response values by the second‐order polynomial model were found to be in good agreement with experimental values (R² = 0.968 and adj‐R² = 0.940). The optimization result showed that the Cr(VI) immobilization efficiency presented the maximal result (90.63%) at the following optimal conditions: ZVIn dosage of 1.5% w/w, reaction time of 60 min, and an initial Cr(VI) concentration of 400 mg/kg.     

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.     

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.     

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.     

Modeling and Optimization of Fluoride and Cadmium Trapping in Phosphogypsum Using Design Methodology

The manufacturing of phosphoric acid from natural calcium phosphate generates a solid residue containing 25–30% humidity. This solid residue (phosphogypsum) generates acidic solution (pH ≈ 2.5) containing several toxic ionic species, that coat its grains. Fluorides and heavy metals such as cadmium are considered the most harmful species contained in the released solution from phosphogypsum. The purpose of this work is to study the trapping of fluorides and cadmium in phosphogypsum as well as effluent neutralization before its discharge into natural recipient. Therefore, calcium carbonate finely ground was added and fully mixed with wet phosphogypsum. A four factors central composite design was used to model and to optimize the operating parameters that govern the process. The studied factors were temperature, reaction time, mass, and grains size of CaCO₃. Considered responses were pH, F⁻, and Cd²⁺ concentrations in the released solution after reaction with CaCO₃. The optimum operating conditions were quite efficient to trap, respectively, 99% Cd²⁺ and 97% of F⁻ with a final pH of 6.66. So an original, easy, simple, and cost effective method to trap some toxic species on phosphogypsum through CaCO₃ addition would likely to be integrated in phosphoric acid manufacturing plant.     

Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q_max) at pH 6 of 85.78 and 49.69 mg g^?1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO₃)₂, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH₂, and CH₃ in aliphatic structures, COO^? and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si? O groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.     

Response Surface Optimization for Removal of Cadmium from Aqueous Solution by Waste Agricultural Biosorbent Psidium guvajava L. Leaf Powder

Response surface methodology (RSM) was applied to study the combined effects of the various parameters namely, pH, biosorbent dosage, cadmium concentration and temperature, and to optimize the process conditions for the maximum removal of cadmium using Psidium guvajava L. leaf powder. In order to obtain the mutual interactions between the variables and to optimize these variables, a 2⁴ full factorial central composite design using RSM was employed. The analysis of variance (ANOVA) of the quadratic model demonstrates that the model was highly significant. The model was statistically tested and verified by experimentation. A maximum cadmium removal of 93.2% was obtained under the following optimum conditions: aqueous cadmium concentration 40.15 mg/L, adsorbent dosage 0.5 g/50 mL solution, pH 5.0, and temperature (35°C). The value of desirability factor obtained was 1.