Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Studies of thermodynamics of phosphomidon on fly ash

Adsorption thermodynamic studies of phosphomidon on fly ash at 25° and 50°C have been analysed as adsorption isotherms, Freundlich equations, K_d values and various other thermodynamic parameters. These data were in close agreement with Freundlich isotherms and yield ‘S’ type isotherms at both the temperatures. Thermodynamic constants (K_o) and standard free energy (ΔG°), enthalpy (ΔH°) and entropy changes (ΔS°) have been calculated for predicting the nature of adsorption.     

The effects of soil properties and temperature on the adsorption isotherms of lead on some temperate and semiarid surface soils of Iran

Sorption of metal ions by soil and clay minerals is a complex process involving different mechanisms, and controlled by different variables that can interact. The aim of this work was to study the retention mechanisms of Pb ions on different soil samples. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The adsorption isotherms of Pb on the soils have been studied at 15, 27 and 37°C. The adsorption data for different soils were fitted into Langmuir and Freundlich models. Temperate soil samples had higher clay content, cation exchange capacity, dichromate (oxidable) organic carbon, total Kjeldahl-nitrogen, biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate, available P and K. Lead adsorption data obtained from semiarid soils against those obtained from temperate soils were better fitted in both Langmuir and Freundlich models. Langmuir constants Q ₀ for Pb adsorption in semiarid soils were considerably lower than those for Pb adsorption in temperate soils. However, the binding energy (K _L) of Pb and Freundlich constant n were higher for data of semiarid soils. The effect of temperature on the Pb adsorption was positive especially in temperate soils; however, soil properties had higher effects on Pb adsorption.     

pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.     

Copper(II) ions’ removal from aqueous solution using green horse-chestnut shell as a low-cost adsorbent

The adsorption of copper(II) ions from aqueous solutions by the green horse-chestnut shell was studied in a batch adsorption system. It was determined how the parameters of the adsorption process, such as time, pH, copper(II) ions concentration and sorbent dose, influence the effectiveness of copper(II) ions’ removal. The adsorption process was fast and equilibrium was established about 10?min, and near 95–97% of Cu(II) ions were removed from aqueous solution. Maximum copper(II) ions’ adsorption occurred at around pH 5. The adsorption kinetics are also described, using pseudo-first-order model and pseudo-second-order model of type 1 and 2. A comparison of the kinetics models on the overall adsorption rate showed that the adsorption system was best described by the pseudo-second-order model of type 1 (r²?=?0.999) for all initial concentrations. Another key part of this study was the use of the Freundlich model to determine the adsorption isotherm and the experimental data were in strong correspondence with this model.     

Thermodynamics of chromium(III) adsorption onto a cation exchanger derived from saw dust of Jack wood

A novel cation exchanger, polymethacrylic acid-grafted saw dust (SD) with spacer group (SP) containing carboxylate functional group at the chain end (SDGPMA-SP-COOH) was prepared from saw dust of Jack wood, and its adsorption equilibrium and thermodynamics of Cr(III) ions were studied at different initial concentrations and temperatures at pH 7.0 using batch technique. Thermodynamic parameters such as change in standard free energy, ΔG ⁰, standard enthalpy, ΔH ⁰ and standard entropy, ΔS ⁰ were determined. The values of isosteric heat of adsorption (ΔH _x ) remain constant at different surface loading of Cr(III) indicating homogeneous surface sites and the absence of lateral interaction between adsorbed ions.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Ackee apple (Blighia sapida) seeds: a novel adsorbent for the removal of Congo Red dye from aqueous solutions

The ability of ackee apple (AA) seeds to remove Congo Red (CR) dye from aqueous solution was investigated. AA was characterised using thermo gravimetric analyser, scanning electron microscopy, Braunauer Emmett Teller, pH_pzc, elemental analysis and Boehm titration. The effects of operational parameters such as adsorbent dosage, contact time, initial dye concentration and solution pH were studied in a batch system. pH has a profound influence on the adsorption process. Maximum dye adsorption was observed at pH 3.0. The reaction was fast, reaching equilibrium in 90 min. Adsorption data were best described by Langmuir isotherm and the pseudo-second-order kinetic model with a maximum monolayer coverage of 161.89 mg·g^?1. Both boundary layer and intraparticle diffusion mechanisms were found to govern the adsorption process. Thermodynamic parameters such as standard free energy change (Δ G ⁰), standard enthalpy change (Δ H ⁰), and standard entropy change (Δ S ⁰) were studied. Values of Δ G ⁰ varied between?30.94 and?36.56 kJ·mol^?1, Δ H ⁰ was 25.61 kJ·mol^?1, and Δ S ⁰ was 74.84 kJ·mol^?1·K^?1, indicating that the removal of CR from aqueous solution by AA was spontaneous and endothermic in nature. Regeneration and reusability studies were carried out using different eluents. AA gave the highest adsorption efficiency up to four cycles when treated with 0.3 M HCl. AA was found to be an effective adsorbent for the removal of CR dye from aqueous solution.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

Adsorption and desorption of tetraalkyllead and dibutyltin compounds on contaminated soils

Adsorption and desorption of di-n-butyltin (IV) (DBT), tetramethyllead (TML), and tetraethyllead (TEL) on four types of soil were studied. Although, all K _d values for desorption are higher than the K _d values for adsorptions, which shows that the adsorption process is reversible, the lower percentages of desorption indicate that very low concentration of these organometallic compounds can be more easily leached from the soil. The adsorption ranging between 48.8% and 88.3% for DBT, between 9.1% and 38.3% for TEL, and between 24.9% and 44.2% for TML was measured. The desorption was obtained between 9.4% and 23.7% for DBT, between 19.3% and 38.9% for TEL, and between 21.5% and 32.7% for TML. These results show that the nonpolar (TML, TEL) organometallic compounds can be easier leached than the ionic forms (DBT). Adsorption kinetics and adsorption as a function of pH were also evaluated. DBT and tetraalkyllead adsorption equilibrium were reached after 12 and 24 h, respectively. The tetraalkyllead is strongly adsorbed at pH 7–8 and DBT at pH 6.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

Development of chitosan-alginate based biosorbent for the removal of p-chlorophenol from aqueous medium

Removal of p-chlorophenol (pCP) from synthetic aqueous solutions was studied through adsorption on a biosorbent developed from chitosan (CS) and sodium alginate (SA), the natural cationic and anionic polysaccharides, respectively. Chitosan-coated sodium alginate beads were prepared and treated with calcium chloride solution in order to improve the stability as well as hydrophobic character. The resulting beads (CS/CA) were characterized using FTIR spectra, scanning electron microscopy (SEM), and BET surface analysis. The efficiency of this biosorbent in removing pCP from aqueous medium was studied under batch equilibrium and dynamic column flow experimental conditions. The binding capacity of the biosorbent was studied as a function of initial pH, contact time, initial concentration of adsorbate and amount of biomass. The data were fitted to pseudo-first-order, pseudo-second-order, and Weber–Morris models and found that the adsorption process followed pseudo-first-order kinetics. Further, the equilibrium data were fitted to Freundlich, Langmiur, and Dubinin–Radushkevich (D–R) adsorption isotherms and the isotherm constants were evaluated for adsorption of pCP. The maximum monolayer adsorption capacity of CS/CA beads was found to be 127 mg g^?1. Column flow results were used to generate breakthrough curves. The experimental results suggested that the chitosan–calcium alginate blended biosorbent was effective for the removal of pCP from aqueous medium.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Heavy metals uptake from aqueous solutions using marine algae (Colpomenia sinuosa): kinetics and isotherms

The adsorption of copper, zinc, cobalt, lead and cadmium ions onto Colpomenia sinuosa was studied as a function of contact time, initial metal ion concentration and initial pH. In addition, desorption studies were performed. Characterisation of this adsorbent was also confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analysis. Batch adsorption experimental data were analysed using Langmuir, Freundlich and Dubinin–Raduschkevich (D–R) adsorption isotherms. The results indicated that the biosorption equilibrium was well described by both the Freudlich and D–R isotherms. Moreover, sorption kinetics was performed and it was observed that equilibrium was reached in<60 min, which could be described by the pseudo-second-order kinetic model for all heavy metals. The sorption of heavy metals onto the biomass was largely dependent on the initial solution pH. The elution efficiency for heavy metal ions desorption from C. sinuosa was determined for 0.1 M HCl, 1.0 M HCl and 1.0 M HNO₃. Desorption efficiency and also adsorption capacity were highest for Pb(II). The results indicate that C. sinuosa has great potential for the removal of heavy metals in an ecofriendly process.     

Potentiometric studies of mixed complexes of cobalt(II) and copper(II) with l‐Asparagine and adenine

A potentiometric titration technique has been used to determine the stability constants for the various complexes of Co(II) and Cu(II) with L‐asparagine and from DNA base, e.g. adenine. Stability constants of ternary systems have been evaluated by the method suggested by Irwing‐Rossotti. In addition, the conditional constants were calculated as a function of pH. The maximum values of the conditional formation constants were found to be in accordance with the mixed‐ligand complex formation constants in a determined pH region. Furthermore, the molar fractions of different species from mixed complexes were calculated by means of formation constants. The values of stability constants of mixed‐ligand complexes at 25°C are as follows: log K= 5.25 for Co(II)‐L‐asparagine‐adenine; log K= 9.30 for Cu(II)‐L‐asparagine‐adenine. The ionic strength was kept constant at I = 0.20 with NaClO₄.     

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (K_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ～15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (R² = 1) and the Freundlich (R² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.     

Cationic dye adsorption onto natural and synthetic zeolites in the presence of Cs+ and Sr2+ ions

Adsorption of diazine dye safranine O (SO) in the presence of Cs⁺ and Sr²⁺ ions was investigated onto natural and synthetic zeolites in order to predict competition of cationic organic species with their radionuclides, which are the main fission products released into the environment. Adsorption of SO was measured up to the 40th day and the surface-diffusion coefficients (D_s) were estimated by applying Nernst–Planck approximation based on a homogeneous-surface-diffusion model. The values of D_s were 10 times higher on natural zeolite than those of synthesized zeolite from fly ash (FA) under hydrothermal conditions. Similarly, distribution coefficients (K_D) were considerably higher on the clinoptilolite-type natural zeolite. The zeolitized product of FA is mainly composed of analcime and sodalite. SO adsorption on natural zeolite was not influenced by Cs⁺ and Sr²⁺ ions, but it decreased at high concentrations on synthetic zeolite. The higher influence of the Sr²⁺ ions on SO⁺ adsorption showed that they compete with each other for the same adsorption sites. These results suggested that natural zeolite cannot be used for remediation of wastewater polluted with Cs and Sr radionuclides in the presence of organic cations, whilst FA zeolite has a potential for Sr removal.     

Removal of congo red and basic violet 1 by chir pine (Pinus roxburghii) sawdust,a saw mill waste: batch and column studies

The efficiency of chir pine sawdust (CPS) for adsorptive removal of the dyes, congo red (CR) and basic violet 1 (BV), from aqueous solution was evaluated using batch and column studies. The equilibrium was attained in 60 min for CR and 45 min for BV. The adsorption of BV obeyed the Langmuir isotherm model while the Freundlich isotherm fitted the equilibrium data of CR adsorption. The Langmuir monolayer adsorption capacities (Q_o) of CPS for BV and CR were 11.3 and 5.8 g kg^?1, respectively. The kinetic data for CR were best fitted to the Lagergren pseudo-first-order model and for BV to the pseudo-second-order model. The intra-particle diffusion was found to be the rate-controlling step for CR adsorption, while the adsorption kinetics of BV were controlled by both intra-particle and liquid-film diffusion. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. The adsorption activation energy (E_a) for CR (124 kJ mol^?1) implied chemical adsorption while that for BV (5.4 kJ mol^?1) indicated physical adsorption. An increase in the Thomas model constant (K_Th) with increasing flow indicated that for both dyes the mass transport resistance decreased during adsorption. Thus, CPS may be an efficient low-cost adsorbent for decolorization of dye-containing wastewaters.     

Heavy-metal adsorption by non-living biomass

The adsorption of some heavy metals onto the walls of harvested, washed, and dried non-living biomass cells of different Pseudomonas strains was studied at optimum experimental conditions using a simplified single component system. The Langmuir adsorption model was found to be a suitable approach to describe the system via multi-step processes. Isotherms measured at 30.0°C and pH 5.5 with [M]_total?=?10–100 mM for tight, reversible Cr⁶⁺(aq), Ni²⁺(aq), Cu²⁺(aq) and Cd²⁺(aq) binding by the cell walls of the investigated biomass fit the Langmuir model and give the pH-independent stoichiometric site capacities ν _i and equilibrium constants K _i for metal binding at specific biomass sites i?=?A, B, C, and D. Tight binding sites A, B, and D of the non-living biomass are occupied by Cr^VI, sites A and C by Ni^II, sites A and D by Cd^II, and only site B by Cu^II. It is concluded that ν _i is a stoichiometric parameter that is independent of the magnitude of K _i for binding site i and that the studied heavy metals selectively and tightly bind at different biomass sites.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.