Adsorption for removal of Cd(II) from effluents

The adsorption of Cd(II) onto wollastonite has been reported. Adsorption increased from 55.7 to 93.6% by decreasing the concentration of Cd(II) from 2.0 x 10^‐4M to 0.5 x 10^‐4M. The rearranged Lagergren equation has been used for dynamic modelling of the process. However, the value of rate constant at 30°C was found to be 3.17 x 10^‐2min^‐1. Equilibrium modelling was carried out using the Freundlich isotherm equation and constants have been calculated. Thermodynamic studies were carried out and values of standard free energy (?G°), enthalpy (?H°) and entropy (AS°) were calculated at various temperatures. Low temperatures favour the uptake of Cd(II) in the process.     

Adsorption of 2,4,6-trichlorophenol by multi-walled carbon nanotubes as affected by Cu(II)

Adsorption equilibrium of 2,4,6-trichlorophenol (TCP) on multi-walled carbon nanotubes (MWCNTs) was investigated to explore the possibility of using MWCNTs for concentration, detection and removal of TCP from contaminated water. The adsorption of TCP on MWCNTs at pH 4 was nonlinear, reversible and best fit by a Polanyi-Manes model. Oxidation treatment increased surface area and introduced hydrophilic carboxylic groups to the defect sites of MWCNTs, hence increased the sorption of TCP and Cu(II) individually. Cu(II) suppressed the sorption of TCP on oxidized MWCNTs15A, but had little effect on as-grown MWCNTs15. TCP had no influence on Cu(II) sorption to either. The mechanisms of Cu(II) suppression effect on TCP adsorption are ascribed to the formation of surface complexes of Cu(II), which was verified by X-ray absorption spectroscopy. Cu(II) exerts a cross-linking effect of functional groups on adjacent tubes, creating a more tightly knit bundle and suppressing the condensation of TCP in the pore spaces between the tubes. The large hydration sphere around surface complexes of Cu(II) may also intrude or shield hydrophilic sites, leading to the “crowding out” of TCP around the Cu(II)-complexed sites.     

Chromate (CrO(4)(2-)) and copper (Cu2+) adsorption by dual-functional ion exchange resins made from agricultural by-products

Ion exchange resins commonly have a single functionality for either cations or anions. Resins that have a dual functionality for both cations and anions are uncommon. The objective of this study was to create dual-functional ion exchange resins derived from soybean hulls, sugarcane bagasse and corn stover. Dual-functional resins were prepared by two separate two-step processes. In the first two-step process, by-products were reacted with a solution of citric acid in order to impart additional negative charge, and then reacted with the cross-linking reagent dimethyloldihydroxyethylene urea (DMDHEU) and a quaternary amine (choline chloride) to add positive charge to the lignocellulosic material. In the second two-step process, the order of reaction was reversed, with positive charge added first, followed by the addition of negative charge. These combined reactions added both cationic and anionic character to the by-products as evidenced by the increased removal from solution of copper (Cu(2+)) cation and the chromate (CrO(4)(2-)) anion compared to unmodified by-products. The order of reaction appeared to slightly favor the functionality that was added last. That is, if negative charge was added last, the resulting resin sequestered more copper ion than a comparable resin where the negative charge was added first and vice-versa. Cu(2+) and CrO(4)(2-) were used as marker ions in a solution that contained both competing cations and anions. The dual-functional resins adsorbed as much as or more of the marker ions compared to commercial cation or anion exchange resins used for comparison. None of the commercial resins exhibited dual-functional properties to the same extent as the by-product-based resins.     

Nitrite reduction with hydrous ferric oxide and Fe(II): Stoichiometry, rate, and mechanism

Fe(II)/Fe(III) oxide is an important redox couple in environmental systems. Recent studies have revealed unique characteristics of Fe(II)/Fe(III) oxide and reactions with oxidizing or reducing agents. Nitrite was used as an oxidizing agent in this study in order to probe details of these reactions and hydrous ferric oxide (HFO) was used as the Fe(III) oxide phase. Abiotic nitrite reduction is a significant global producer of nitric oxide (a catalyst for production of tropospheric ozone) and nitrous oxide (a greenhouse gas and contributor to stratospheric ozone depletion). All experiments were conducted at pH 6.8 using a strictly anoxic environment with mass-balance measurements for Fe(II). Oxidation of Fe(II) was negligible in the absence of HFO. The reaction was fast in the presence of HFO and was described by d[Fe(II)]/dt = −k_overall [Fe(II)_diss] [Fe(II)_solid-bound] [NO₂⁻] (k_overall = 2.59 × 10⁻⁷ μM⁻² min⁻¹) for Fe(II)/Fe(III) molar ratios less than 0.30. The reaction was inhibited for higher Fe(II)/HFO ratios. The concentration of solid-bound Fe(II) was constant after an initial equilibration period and the reaction stopped when dissolved Fe(II) was depleted even though substantial solid-bound Fe(II) and nitrite remained. The results regarding rate-dependence and conservation of solid-bound Fe(II) and inhibition of reaction at high Fe(II)/Fe(III) ratios were similar to our earlier results for the Fe(II)/HFO/O₂ system [Park, B., Dempsey, B.A., 2005. Heterogeneous oxidation of Fe(II) on ferric oxide at neutral pH and a low partial pressure of O₂. Environmental Science and Technology 39(17), 6494-6500.].     

Kinetic analysis of palladium(II) adsorption process on condensed-tannin gel based on redox reaction models

We have developed a novel recovery system of palladium (Pd) from wastes such as spent catalysts or scraps, using tannin gel particles synthesized from condensed-tannin molecules. The Pd(II) ionic species are reduced to metallic Pd(0) on the network of the tannin gel: a two-electron transfer from the tannin gel to Pd(II). The kinetic study of the electron transfer was performed with a multiple reaction model containing an intermediate step (formation of a ligand-substituted Pd(II)-tannin inner sphere complex), resulting in a better fit with the experimental results than with the single reaction model (outer sphere redox reaction), which means that the inner sphere redox mechanism is an appropriate reaction model for the Pd(II) adsorption process. Because the intermediate is included in the adsorption amount, the adsorption process can be divided into two steps: fast adsorption by the ligand substitution at the initial stage and slow adsorption by the subsequent redox reaction after the ligand substitution reaches an equilibrium state, with different adsorption rates between the Pd(II) ionic species (PdCl(+)>PdCl(2)>PdCl(3)(-),PdCl(4)(2-)).     

The removal of hexacyanoferrate(II) and (III) ions in dilute aqueous solution by activated carbon

The removal of iron cyano-complex ions [hexacyanoferrate(II) and (III) ions] in a dilute aqueous solution by activated carbon was investigated. The maximum adsorption of iron cyano-complex ions on activated carbon occurred at pH around 3. The hexacyanoferrate(III) ion was more adsorbable than the hexacyanoferrate(II) ion. Activated carbon promoted the oxidation of hexacyanoferrate(II) ion to (III) ion with dissolved oxygen in an acidic solution and the reduction of hexacyanoferrate(III) ion to (II) ion in an alkaline solution. The iron cyano-complex ion adsorbed on activated carbon could be eluted with higher concentrated acidic and alkaline solutions. The degree of elution decreased with an increase in potassium hydroxide concentration, since parts of the iron cyano-complexes on activated carbon were decomposed to form the iron hydroxide and the hexacyanoferrate(II) ion with an alkaline solution. The behavior of iron cyano-complexes in the presence of activated carbon, in the lower pH range (pH < 1) and at higher temperatures (80°C), was discussed.     

Removal of Cu(II) from aqueous solutions by adsorption process with anatase-type titanium dioxide

The experiment was performed in the reactor with suspended anatase-type titanium dioxide particles. The adsorption amount increased rapidly with an increasing pH value from pH 2 to 5 and remained constant over pH 5. The adsorption amount of Cu(2+) increased with temperature from 15 degrees C to 40 degrees C. The adsorption equilibrium constant (K(ads)) was 0.854 and adsorption isotherm of Cu(2+) adsorption on titanium dioxide was more suitable in Langmuir adsorption isotherm than in Freundlich isotherm. The adsorption rate was rapid with an increasing number of UV lamps of 254 nm.     

Deploying a metal adsorbent in situ: a technique for indicating bioavailable Cd(II) in marine waters

This paper reports a study into the deployment of a metal adsorbent in situ to estimate bioavailable Cd(II) in marine waters. Eight adsorbents were screened in the laboratory to test their ability to accumulate Cd(II) from deionised water and artificial seawater, and an oxidised activated carbon was selected for further investigation. The adsorption isotherm at Cd(II) concentrations 0.16-38 microgl(-1) and at salinity 15 followed the Freundlich equation. The adsorbent was contained in nylon bags (pore size 35 microm) and dialysis tubes (membrane pore size 2 nm) to produce deployable devices and to investigate the effect of housing material on Cd(II) accumulation. The devices were tested in the laboratory and deployed at four field sites for up to 3 weeks. The adsorbent in the nylon bags reached equilibrium towards the end of this period and the measured contents were in good agreement with expected contents predicted from known seawater Cd(II) concentrations and the adsorption isotherm. The dialysis tubes accumulated significantly lower amounts of Cd(II) than the nylon bags, probably due to an initial lag as Cd(II) diffused into the dialysis bag and due to biofouling which reduced diffusion. The relationship between concentrations of Cd(II) accumulated by the mussels (indicating the bioavailable Cd(II) fraction) and the devices at different field sites could be described by the Freundlich model. The goodness of fit of this relationship was better for the dialysis tubes than the nylon bags. The adsorbent in the nylon bags may have collected small particles from seawater which affected the Cd(II) analysis. Both devices demonstrate potential as indicators of the relative bioavailable fraction of Cd(II) to Mytilus edulis in marine waters.     

Determination of the complexing properties of drinking waters toward copper(II) and aluminium(III) by ligand titration

The complexing capacity of some drinking waters for aluminium(III) and copper(II) is determined by a ligand titration with metal ions based on the use of complexing resins. The resins used in the titration are the iminodiacetic resin Chelex 100, the carboxylic resin Amberlite CG50 and the anionic exchange resin AG1X8. They allow the detection of ligands forming complexes of different stability with the metal ions used for the titration, since they have different sorbing properties. After equilibration with the resin, the concentration of the free metal ion in solution is evaluated from the concentration of sorbed metal ion and from the quantity K^*, which is the ratio of the concentration of the metal ion sorbed on the resin to the free metal ion in solution. It strongly depends on the conditions, but it can be evaluated, at the considered conditions, from the sorption equilibria of the metal ion on the resin. The concentration of the ligands in solution and the conditional stability constant are obtained from the Ruzik linearization procedure. Very strong ligands of copper(II) and aluminium(III) were detected in a tap water sample at concentrations ranging from 10⁻⁷ to 10⁻⁶ mol kg⁻¹, and forming complexes having conditional complexation constants K_cI=2.3×10¹⁷ (pH=6.77) and 4.5×10¹⁶ (pH=6.24), respectively, for copper(II) and aluminium(III). Weaker ligands were detected using the less strongly sorbing resins Amberlite CG50 and AG1X8, but at a concentration equal to that of the strong ligands. This was ascribed to the presence of competing metals in solution, not sorbed by the weak resins. Two other drinking waters had completely different complexing properties both towards copper(II) and aluminium(III), containing much weaker ligands.     

Multi-component adsorption of Ag(I), Cd(II) and Cu(II) by natural carbonaceous materials

Adsorption of silver, cadmium and copper from aqueous solutions by natural carbonaceous materials was investigated. The studied series of natural materials (spruce wood, pine bark, cork, peat, fusinite, lignite, oxidised lignite, bituminous coal and anthracite) was extended to include industrial carbon-rich materials: coke, activated carbon F-400 and Multisorb 100. Adsorption was tested on a single-component system and on the binary and ternary mixtures. All the materials used differ in their ability to adsorb selected metals. The adsorption of metals is significantly affected by the presence of other ions in solution. Total metal uptake was considerably higher in a mixture than single-ion adsorption. Chemical reactions, such as precipitation and reduction of metallic silver, play a role in metal uptake by bituminous coal, coke and activated carbon.     

Mechanism of Cu(II)-catalyzed monochloramine decomposition in aqueous solution

The decomposition of monochloramine, which is commonly used as a secondary disinfectant at water treatment plants to reduce the formation of disinfection byproducts, always occurs in water and can be accelerated by certain catalytic substances. This work was to investigate the mechanism of monochloramine decomposition catalyzed by Cu(II) in aqueous solution. Ultraviolet (UV) spectral results showed that either Cu(II) addition or pH decrease would significantly promote the transformation of monochloramine to dichloramine. A copper intermediate, Cu(I), was extracted from the NH₂Cl-Cu(II) solution by solid-phase extraction and identified by X-ray photoelectron spectroscopy (XPS). Electron spin resonance (ESR) results showed that hydroxyl radical (·OH) and amidogen radical (·NH₂) were generated in the reaction between monochloramine and Cu(II). These radical intermediates also contributed to monochloramine decomposition. Based on the experimental results, the reaction mechanism for Cu(II)-catalyzed monochloramine decomposition was proposed which consisted of two pathways: 1) direct catalysis in which Cu(II) acts as a Lewis acid to accelerate monochloramine decomposition to dichloramine (major pathway); and 2) indirect catalysis in which the active radical intermediates (·OH and ·NH₂) react with monochloramine and lead to its decomposition (minor pathway).     

Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric acid-containing wastewater

Heavy metal-contaminated soil and wastewater have been attracting an increasing amount of attention due to the potential threat to the surrounding environment and human health. Thus, in this study, citric acid (CA) and citric acid-containing wastewater (CACW) were selected for an evaluation of the influence of the contamination level of the soil, the concentration of citric acid, the contact time, the soil pH, and the ionic interaction on the desorption characteristics of three heavy metals (i.e., Cr(III), Mn(II), and Ni(II)). According to the experimental results, a high concentration of citric acid, an acidic condition, a low level of contamination, and a lengthy contact time were found to be beneficial for desorbing the heavy metals from the contaminated soil. Based on the experimental and calculated results, the H⁺ ions and organic ligands made substantial contributions to the release and adsorption of the heavy metals. The metal ions on the low selectivity sorption sites were leached out earlier than those on the high selectivity sorption sites. The removal percentages of Cr(III), Mn(II), and Ni(II) using CA with a contact time of 6?h were 39.9%, 77.0%, and 62.8%, respectively. By using the CACW as a desorbent, the removal percentages of Cr(III), Mn(II), and Ni(II) with a contact time of 6?h reached 21.4%, 26.9%, and 63.4%, respectively. This suggests a promising practical application of CACW for removing heavy metals from contaminated soil.     

Adsorption of Cu(II) from industrial liquid waste on Na-bentonite and Al-PILC following a full factorial design

The paper reports a study of the performance of Maghnia bentonite in a purified and modified state for the removal of Cu(II) from industrial liquid waste in the region of Oran (North West Algeria). Bentonite was firstly treated to produce a Na-bentonite, then modified with an aluminum solution containing molar ratio OH/Al of 1.8 and finally calcined at 450 °C. The polymer [AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺ formed in solution was adsorbed by surface complexation on the bentonite, which is known to have a high capacity to fix metal cations. The prepared materials were characterized by DRX, BET and EDX. In order to find the optimum conditions, a full factorial design of 2⁴ allowed us to determine the main effects and interactions of the factors studied: pH, mass of materials, contact time and temperature. The results obtained show that the best rate of adsorption of copper requires a pH = 10, a mass = 0.8 g, a stirring time = 80 min, and a temperature = 25 °C. The adsorption capacity of treated bentonite increased considerably from 4.147 mg/g for Na-bentonite to 7.173 mg/g for pillared aluminum bentonite. This shows the strong adsorption of copper compared with Na-bentonite, caused by its high surface area.     

Observations on the use of iron(II) complexing agents to fractionate the total filterable iron in natural water samples

Analysis of filtered natural water samples using Fe(II) complexing agents (bathophenanthrolinedisulphonic acid, 2,2′-dipyridyl, ferrozine, TPTZ) and acetic acid-sodium acetate buffer (pH 4.6) showed that the absorbance of the iron(II) complex increased with time both in the presence and the absence of a reducing agent (ascorbic acid, hydroxylammonium chloride). Exposure of the samples to 0.1 M HCl (pH 1.3) for 1 h prior to the addition of the complexing reagents resulted in a stable iron concentration which was designated the acid-extractable fraction of the total filterable iron. The results have implications for the complexometric determination of iron fractions other than total iron after acid digestion.     

Removal of arsenic from water: Effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process

A novel KMnO₄–Fe(II) process was developed in this study for As(III) removal. The optimum As(III) removal was achieved at a permanganate dosage of 18.6 μM. At the optimum dosage of permanganate, the KMnO₄–Fe(II) process was much more efficient than the KMnO₄–Fe(III) process for As(III) removal by 15–38% at pH 5–9. The great difference in As(III) removal in these two processes was not ascribed to the uptake of arsenic by the MnO₂ formed in situ but to the different properties of conventional Fe(III) and the Fe(III) formed in situ. It was found that the presence of Ca²⁺ had limited effects on As(III) removal under acidic conditions but resulted in a significant increase in As(III) removal under neutral and alkaline conditions in the KMnO₄–Fe(II) process. Moreover, the effects of Ca²⁺ on As(III) removal in the KMnO₄–Fe(II) process were greater at lower permanganate dosage when Fe(II) was not completely oxidized by permanganate. This study revealed that the improvement of As(III) removal at pH 7–9 in the KMnO₄–Fe(II) process by Ca²⁺ was associated with three reasons: (1) the specific adsorption of Ca²⁺ increased the surface charge; (2) the formation of amorphous calcium carbonate and calcite precipitate that could co-precipitate arsenate; (3) the introduction of calcium resulted in more precipitated ferrous hydroxide or ferric hydroxide. On the other hand, the enhancement of arsenic removal by Ca²⁺ under acidic conditions was ascribed to the increase of Fe retained in the precipitate. FTIR tests demonstrated that As(III) was removed as arsenate by forming monodentate complex with Fe(III) formed in situ in the KMnO₄–Fe(II) process when KMnO₄ was applied at 18.6 μM. The strength of the “non-surface complexed” As–O bonds of the precipitated arsenate species was enhanced by the presence of Ca²⁺ and the complexation reactions of arsenate with Fe(III) formed in situ in the presence or absence of Ca²⁺ were proposed.     

Equilibrium and kinetic modelling of Cd(II) biosorption by algae Gelidium and agar extraction algal waste

In this study an industrial algal waste from agar extraction has been used as an inexpensive and effective biosorbent for cadmium (II) removal from aqueous solutions. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction. Equilibrium data follow both Langmuir and Redlich-Peterson models. The parameters of Langmuir equilibrium model are q(max)=18.0 mgg(-1), b=0.19 mgl(-1) and q(max)=9.7 mgg(-1), b=0.16 mgl(-1), respectively for Gelidium and the algal waste. Kinetic experiments were conducted at initial Cd(II) concentrations in the range 6-91 mgl(-1). Data were fitted to pseudo-first- and second-order Lagergren models. For an initial Cd(II) concentration of 91 mgl(-1) the parameters of the pseudo-first-order Lagergren model are k(1,ads)=0.17 and 0.87 min(-1); q(eq)=16.3 and 8.7 mgg(-1), respectively, for Gelidium and algal waste. Kinetic constants vary with the initial metal concentration. The adsorptive behaviour of biosorbent particles was modelled using a batch reactor mass transfer kinetic model. The model successfully predicts Cd(II) concentration profiles and provides significant insights on the biosorbents performance. The homogeneous diffusivity, D(h), is in the range 0.5-2.2 x10(-8) and 2.1-10.4 x10(-8)cm(2)s(-1), respectively, for Gelidium and algal waste.     

Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles

Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (σ(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water.     

Removal and recovery of Cr(VI) from polluted ground waters: a comparative study of ion-exchange technologies

The focus of this work has been the study of Cr(VI) removal from ground waters and the simultaneous concentration for its reuse using three different technological alternatives: anion-exchange resins, liquid-liquid extraction assisted by hollow fibre membranes and emulsion pertraction. The viability of the considered objectives, i.e., Cr(VI) separation (<0.5 g/m3) and concentration for reuse (>20,000 g/m3) has been checked and a comparative analysis of the three technologies has been performed. Although the flexibility and ease of operation of non-dispersive solvent extraction, anion-exchange resins and emulsion pertraction lead to higher velocities of chromium removal, yet still maintaining similar concentration efficiencies.     

Decolourization performance and mechanism of leachate secondary effluent using Poly‐aluminium(III)–magnesium(II) sulphate

Poly‐aluminium(III)–magnesium(II) sulphate (PMAS) was used to remove the colour from the secondary effluent of landfill leachate and the decolourization mechanism was researched. The results indicated that the decolourization efficiency using PMAS was better than the decolourization that occurred using other traditional coagulants, with a colour removal >90%. X‐ray diffraction and infrared spectrometry showed that PMAS was probably a type of macromolecular composite polymer of aluminium and magnesium that was based on –OH bonds. The coagulation mechanism of PMAS was primarily charge neutralization and coprecipitation netting, with charge neutralization being the dominant mechanism at low doses. In addition, the flocculation behaviour differed in response to various pH values of wastewater at high doses. Specifically, flocculation was primarily driven by charge neutralization at a low pH and coprecipitation netting at a high pH, while it occurred via a combination of these procedures under neutral conditions.