Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isothermrevealed that the equilibriumconstant derived from the Langmuir kinetic model, K_S-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, K_S-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isothermmodel (MLImodel) incorporating pH factor were developed. The MLKmodel was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO₂ at pH 3.2 or 3.3 to get the values of K_S-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of K_S-Langmuirwere obtained. The values of K_S-kinetic and K_S-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with K_S-kinetic constants could predict the adsorption edges of heavy metals on MnO₂ very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO₂ at various pH levels could be predicted reasonably well by the MLI model with the K_S-kinetic constants.     

Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH₂-Mn-SBA- 15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganeseloaded SBA-15 (Mn-SBA-15) and used as a Cu²⁺ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N₂ adsorption/ desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH₂-Mn-SBA-15. The orderedmesoporous structure of SBA-15 was remained aftermodification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu²⁺ on NH₂-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH₂-Mn-SBA-15 for Cu²⁺ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu²⁺ by NH₂-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu²⁺. The NH₂-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH₂-Mn-SBA-15 could be regenerated by acid treatment without altering its properties.     

Floatability of polymer materials modulated by frothers

Flotation tests of 35 polymer materials were carried out to investigate their floatability modulated by frothers. Results of flotation tests demonstrated that polymer resins and soft PVC showed high floatability, floatability of hard PVC plastics was relatively low and was related to the frothers, and there exists significant difference in the floatability of different post-consumer plastics. Flotation rate of post-consumer plastics varies from 0% to 100%. Furthermore, three-category low-energy surface (LES) was defined based on the hydrophile index of the materials involved in this paper, and an adsorption model was proposed to explain the results of flotation and to discuss the floatability of polymer materials modulated by frothers. Frother molecules are prone to adsorb on the surface of bubble rather than LES at relatively low concentration, bubble adsorbed by frother molecules is prone to approach first-category LES rather than third-category LES, and the structure of liquid film is formed on the first-category LES at large concentration. Floatability of polymer materials modulated by frothers is further discussed: frothers increase the floatability of the first-category LES but decrease the floatability of the third-category LES, while the floatability of the second-category LES is related to the type of frothers.     

Study of Ni adsorption on NKF-6 zeolite

The adsorption of ⁶³Ni from aqueous solutions using NKF-6 zeolite was investigated by a batch technique under ambient conditions. The adsorption was investigated as a function of contact time, pH, ionic strength, foreign ions, humic substances (FA/HA) and temperature. The kinetic adsorption was well described by the pseudo-second-order rate equation. The adsorption of ⁶³Ni on NKF-6 zeolite was strongly dependent on pH and ionic strength, and the adsorption of ⁶³Ni increased with increasing NKF-6 zeolite content. At low pH values, the presence of FA enhanced the adsorption of ⁶³Ni on NKF-6 zeolite, but the presence of HA had no drastic effect. At high pH values, the presence of FA or HA decreased the adsorption of ⁶³Ni on NKF-6 zeolite. The adsorption isotherms were well represented by the Langmuir model. The thermodynamic parameters (i.e., ΔH⁰, ΔS⁰and ΔG⁰) for the adsorption of ⁶³Ni were determined from the temperature dependent isotherms at 293.15, 313.15 and 333.15 °K, respectively, and the results indicate that the adsorption reaction was favored at high temperature. The results suggest that the adsorption process of ⁶³Ni on NKF-6 zeolite is spontaneous and endothermic.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Relationship between Pd oxidation states on TiO2 and the photocatalytic oxidation behaviors of nitric oxide

This study has been undertaken to investigate the relationship between Pd oxidation states on TiO₂ photocatalysts and their photocatalytic oxidation behaviors of NO. Three types of Pd-modified TiO₂ with different Pd oxidation states were prepared by wet impregnation method, neutralization method and photodeposition method, respectively. And these Pd-modified photocatalysts were characterized by X-ray diffraction analysis, X-ray photoelectron spectrum analysis (XPS), UV–Vis diffuse reflectance spectra and temperature programmed desorption (TPD). It was found from XPS results that the dominant oxidation states of Pd on these Pd-modified TiO₂ catalysts were Pd²⁺, PdO, and Pd⁰, respectively. NO-TPD results showed that the NO adsorption capacity was improved greatly by the modification of Pd²⁺ ions. The activity tests showed that Pd-modified TiO₂ by a wet impregnation method increased photocatalytic activity compared to pure TiO₂ (Degussa P25). It was concluded that Pd²⁺ ions on as-prepared TiO₂ catalysts provided key contributions to the improvement of photocatalytic activity. However, Pd⁰ and PdO deposits on TiO₂ almost had no positive effect on NO oxidation. The mechanism of photocatalytic oxidation of NO in gas phase over Pd-modified TiO₂ was also proposed.     

Trapping and decomposing of color compounds from recycled water by TiO2 coated activated carbon

Five types of commercially available activated carbons (ACs) were coated with TiO₂ nanoparticles prepared using a sol–gel method. Color and trace organics remaining in the actual treated effluent were adsorbed by TiO₂ coated ACs. The absorbed organic compounds were then decomposed using a photocatalytic process, and the ACs were regenerated for reuse. The efficiency of the process was assessed by the characterization of true color and A₂₅₄ (the organics absorption at the wavelength of 254 nm) at the beginning and the end of the experiment. The effects of UV light source, UV irradiation time, hydrogen peroxide and ultrasound on the efficiency of photocatalytic regeneration were also investigated. Significant differences in the efficiency were observed between uncoated ACs and TiO₂ coated samples. Among the 5 types of ACs tested, AC-3, AC-4 and their coated ones achieved better efficiency in color and A₂₅₄ removal, with around 90% or more color and A₂₅₄ being removed within 1 h of treatment. The data obtained in this study also demonstrated that the photocatalytic process was effective for decomposing the adsorbed compounds and regenerating the spent TiO₂/AC-3. Finally, it was found that this regeneration process could be greatly enhanced with the assistance of H₂O₂ and ultrasound by reducing the required regeneration time.     

Rice husk ash as an effective adsorbent: evaluation of adsorptive characteristics for Indigo Carmine dye

Present study explored the adsorptive characteristics of Indigo Carmine (IC) dye from aqueous solution onto rice husk ash (RHA). Batch experiments were carried out to determine the influence of parameters like initial pH (pH(0)), contact time (t), adsorbent dose (m) and initial concentration (C(0)) on the removal of IC. The optimum conditions were found to be: pH(0)=5.4, t=8h and m=10.0 g/l. The pseudo-second-order kinetic model represented the adsorption kinetics of IC on to RHA. Equilibrium isotherms were analyzed by Freundlich, Langmuir, Temkin and Redlich-Peterson models using a non-linear regression technique. Adsorption of IC on RHA was favorably influenced by an increase in the temperature of the operation. The positive values of the change in entropy (DeltaS(0)) and heat of adsorption (DeltaH(0)); and the negative value of change in Gibbs free energy (DeltaG(0)) indicate feasible and spontaneous adsorption of IC on to RHA.     

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.     

Assessment of surface area normalisation for interpreting distribution coefficients (Kd) for uranium sorption

Adsorption of radionuclides on soils and sediments is commonly quantified by distribution coefficients (K_d values). This paper examines the relationship between K_d values for uranium(VI) adsorption and the specific surface area (SSA) of geologic materials. We then investigate the potential applicability of normalising uranium (U) K_d measurements using the SSA, to produce ‘K_a values’ as a generic expression of the affinity of U for the surface. The data for U provide a reasonably coherent set of K_a values on various solid phases, both with and without ligands. The K_a representation provides a way of harmonising datasets obtained for materials having different specific surface areas, and accounting for the effects of ligands in different systems. In addition, this representation may assist in developing U sorption models for complex materials. However, a significant limitation of the K_a concept is that sorption of radionuclides at trace levels can be dominated by interactions with specific surface sites, whose abundances are not reflected by the SSA. Therefore, calculated K_a values should be interpreted cautiously.