Sorption of heavy metal ions from aqueous solution by a novel cast PVA/TiO2 nanohybrid adsorbent functionalized with amine groups

Sorption of Cd(II), Ni(II) and U(VI) ions onto a novel cast PVA/TiO₂/APTES nanohybrid adsorbent with variations in adsorbent dose, pH, contact time, initial metal concentration and temperature has been investigated. The adsorbent were characterized by SEM and FTIR analysis. BET surface area, pore diameter and pore volume of adsorbent were 35.98 m² g⁻¹, 3.08 nm and 0.059 cm³ g⁻¹, respectively. The kinetic and equilibrium data were accurately described by the double-exponential and Freundlich models for all metals. The maximum sorption capacities were 49.0, 13.1 and 36.1 mg g⁻¹ for Cd(II), Ni(II) and U(VI) ions with pH of 5.5, 5 and 4.5, respectively. Thermodynamic studies showed that the sorption process was favored at higher temperature. The adsorbent can be easily regenerated after 5 cycles of sorption–desorption.     

A preliminary evaluation on the use of the cyclam functionalized resin for the noble metals sorption

A new resin has been prepared through a reaction between the vinylbenzyl chloride–divinylbenzene copolymer and the 1,4,8,11-tetraazacyclotetradecane (cyclam). This resin has been investigated after the characterization of the FTIR, batch and the dynamic sorption behavior of Au(III), Pt(IV) and Pd(II) ions took place. The sorption has been optimized with respect to HCl solutions. The maximum sorption properties were achieved from the solution of 0.1 M HCl. The sorption of Au(III), Pt(IV) and Pd(II) ions during a dynamic procedure in the presence of the 20-fold excess metals i.e. Cu, Fe, Ni resulted in an outcome of up to 400 mg of noble metals per gram of dry resin. The study of the noble metal loading was carried out over a wide range of the HCl concentration and in media of various multicomponent solutions of common metals.     

Temperature-swing adsorption of precious metal ions onto poly(2-(dimethylamino)ethyl methacrylate) gel

The temperature-swing adsorption (TSA) of heavy metal ions onto 2-(dimethylamino)ethyl methacrylate (DMAEMA) gel has been examined. The DMAEMA gel adsorbs precious metal ions (Pt(IV), Au(III), and Pd(II)) in HCl aqueous media as a result of the electrostatic interactions between the protonated amino groups in the gel and the anionic chloro complexes, while it is inactive against Cu(II) and Ni(II) cations. The amount of Pt(IV) ions adsorbed onto the DMAEMA gel decreases linearly with an increase in temperature. The TSA operation was successfully carried out; the DMAEMA gel repeatedly adsorbed and desorbed Pt(IV) ions in the temperature-swing operation between 20 °C and 60 °C. The TSA technique using the DMAEMA gel is simple, environment-friendly, and potentially applicable in various separation processes for precious metals in industries.     

Studies on uptake behavior of Hg(II) and Pb(II) by amine modified glycidyl methacrylate–styrene–N,N′-methylenebisacrylamide terpolymer

The removal of mercury and lead ions from aqueous solutions investigated by ethylenediamine, diethylenetriamine and tetraethylenepentamine functionalized polymeric adsorbent. The adsorbent was prepared by amination of terpolymer synthesized from glycidylmethacrylate, styrene and N,N′-methylenebisacrylamide. In the single metal species system (only mercury or lead ions are present) poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA), and poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA) were found to adsorb lead or mercury ions with a slightly higher adsorption uptake capacity for lead than mercury ions. Among the three functionalized polymers poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA) shows faster and higher adsorption capacity than poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA). The natural pH of both the metal ions was found to be most suitable for uptake. The uptake of Hg(II) and Pb(II) ions was investigated by using batch technique. The maximum adsorption capacities of Pb ions were predicted to be 4.74, 4.76 and 4.73 mmol/g and the maximum Hg(II) ion uptakes were found to be 4.76, 4.80 and 4.21 mmol/g respectively for PGMA–EDA, PGMA–DETA and PGMA–TEPA resins at their natural pH. The uptakes of Hg(II) and Pb(II) ions on the resins were found to follow Langmuir adsorption isotherm and pseudosecond order kinetics.     

Extraction of cadmium from solutions containing various heavy metal ions by Amberlite LA-2

In present study, selective extraction of cadmium from acidic leach solutions, containing various heavy metal ions, by emulsion liquid membrane (ELM) is studied. For this reason, the zinc plant copper cake was leached with sulfuric acid and main acidic leach solution containing Zn(II), Cu(II), Fe(II), Cd(II), Co(II) and Ni(II) ions was obtained. After Zn(II), Cu(II), Fe(II) and Cd(II) ions in the acidic leach solution were separated, the important parameters influencing the extent of cadmium extraction were investigated and optimum conditions were determined. Cadmium extraction was influenced by number of parameters like initial metal ion concentration, mixing speed, phase ratio, extractant concentration, surfactant concentration, the stripping solution type and concentration, and the feed solution acid concentration. The optimum values of parameter above mentioned were used and cadmium in the acidic leach solution containing 650 mg Cd/L, 365 mg Co/L, 535 mg Ni/L, and 1260 mg Zn/L was almost completely extracted within 10 min. The results showed that it is possible to extract 99% of cadmium after 10 min contact time by using ELM from aqueous solutions, containing Fe(II), Al(III), Cu(II), Zn(II), Pb(II), Co(II) and Ni(II) ions, at the optimum operating conditions.     

Sulfonamide based polymeric sorbents for selective mercury extraction

New polymeric resin with sulfonamide pendant functions have been prepared for the selective extraction of mercuric ions. This polystyrene sulfonamide resin with a 3.5 mmol/g total nitrogen content is able to selectively sorb mercury from aqueous solutions.The mercury sorption capacity of the resins are around 1.71 mmol/g for acetyl sulfonamide resin and 2.9 mmol/g for methanesulfonyl sulfonamide resin under non-buffered conditions. The experiments performed under identical conditions with some metal ions reveal that Cd(II), Pb(II), Zn(II) and Fe(III) ions are also extractable in low quantity (0.05–0.1 mmol/g). The mercury-loaded polymers (acetyl sulfonamide and methanesulfonyl sulfonamide) may be quantitatively regenerated with hot acetic acid and 4 M HNO₃.     

Chitosan modified with Reactive Blue 2 dye on adsorption equilibrium of Cu(II) and Ni(II) ions

This study aimed at immobilizing Reactive Blue 2 (RB 2) dye in chitosan microspheres through nucleophilic substitution reaction. The adsorbent chemical modification was confirmed by Raman spectroscopy and thermogravimetric analysis. This adsorption study was carried out with Cu(II) and Ni(II) ions and indicated a pH dependence, while the maximum adsorption occurred around pH 7.0 and 8.5, respectively. The pseudo second-order kinetic model resulted in the best fit with experimental data obtained from Cu(II) (R = 0.997) and Ni(II) (R = 0.995), also providing a rate constant, k₂, of 4.85 × 10⁻⁴ and 3.81 × 10⁻⁴ g (mg min)⁻¹, respectively, thus suggesting that adsorption rate of metal ions by chitosan-RB 2 depends on the concentration of ions on adsorbent surface, as well as on their concentration at equilibrium. The Langmuir and Freundlich isotherm models were employed in the analysis of the experimental data for the adsorption, in the form of linearized equations. Langmuir model resulted in the best fit for both metals and maximum adsorption was 57.0 mg g⁻¹ (0.90 mmol g⁻¹) for Cu(II) and 11.2 mg g⁻¹ (0.19 mmol g⁻¹) for Ni(II). The Cu(II) and Ni(II) ions were desorbed from chitosan-RB 2 with aqueous solutions of EDTA and H₂SO₄, respectively.     

Pb(II) sorption on molecular sieve analogues of MCM-41 synthesized from kaolinite and montmorillonite

Mesoporous molecular sieves were prepared with montmorillonite and kaolinite as silica sources, respectively, (denoted as P-M and P-K) by a hydrothermal method. The two prepared materials were characterized by XRD, FTIR and N₂ adsorption–desorption. The results indicated that both P-M and P-K are typical mesoporous molecular sieves with high specific surface areas. Sorption of Pb(II) from aqueous solution to P-M and P-K was studied by using a batch technique. The effect of contact time, pH and temperature on the sorption of Pb(II) to P-M and P-K was investigated. A simplified surface complexation model was used to simulate the complexation of Pb(II) ions onto molecular sieves. The results suggested that sorption of Pb(II) was strongly dependent on pH values. Kinetics of sorption showed that the pseudo-second-order kinetic model held for the sorption process. Equilibrium modeling showed that the sorption of Pb(II) was fitted well by the Langmuir isotherm model. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated from the sorption of Pb(II) at three different temperatures of 283 K, 303 K and 333 K. The sorption reaction was endothermic and the process was favored at high temperature. The results indicated that both P-M and P-K are suitable materials for removal of Pb(II) from large volumes of aqueous solutions.     

Removal of heavy metals and neutralisation of acid mine drainage with un-activated attapulgite

Unactivated attapulgite was characterised and utilised as an adsorbent for the removal of heavy metal and neutralisation of acid mine drainage (AMD) from a gold mine. Adsorption experiments were carried out by agitation of a fixed amount of attapulgite with a fixed volume of AMD in a thermostatic shaker for varying times. Attapulgite showed that it can neutralise acid mine drainage as the pH after 4 h was 7.11. The results showed that metal ion removal after 4 h was 100% for Cu(II) and Fe(II), 93% for Co(II), 95% for Ni(II) and 66% for Mn(II) using a 10% (w/v) attapulgite loading. The experimental data best fit the Langmuir Isotherm with maximum adsorption capacities for Cu(II), Co(II), Mn(II), Fe(II) and Ni(II) being 0.0053, 0.0044, 0.0019, 0.01, and 0.0053 mg/g, respectively. The adsorption process fitted well the pseudo first order kinetics for Co(II) and Cu(II) and pseudo second order for Ni(II), Mn(II) and Fe(II). Thermodynamic data show that Cu(II), Co(II), Fe(II) and Ni(II) adsorption was thermodynamically spontaneous whilst Mn(II) was not thermodynamically spontaneous. The process is endothermic for Cu(II), Co(II), Mn(II), and Ni(II) and exothermic for Fe(II). Spent attapulgite (attapulgite that has already been used to remove metals) could be reused twice without regeneration.     

Simultaneous preconcentration of Cd(II), Cu(II) and Pb(II) on Nano-TiO2 modified with 2-mercaptobenzothiazole prior to flame atomic absorption spectrometric determination

Nano-TiO₂ modified with 2-mercaptobenzothiazole (MBT) was investigated as a new adsorbent for preconcentration of Cd(II), Cu(II) and Pb(II). The metal ions are adsorbed onto nano-TiO₂-MBT, eluted by nitric acid and determined by flame atomic absorption spectrometry. The parameters affecting the adsorption were investigated. Under optimized conditions, the calibration curves were linear in the range of 0.2–25.0, 0.2–20.0, and 3.0–70.0 ng mL⁻¹ for cadmium, copper and lead, respectively. The limits of detection for Cd(II), Cu(II) and Pb(II) were 0.12, 0.15 and 1.38 ng mL⁻¹, respectively. The method was applied to determination of Cd(II), Cu(II) and Pb(II) in water and ore samples.     

Adsorption properties of poly(acrylaminophosphonic-carboxyl-hydrazide)type chelating fiber for heavy metal ions

In this article, the adsorption properties of poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibers for Cu(II), Cd(II), Co(II), Mn(II), Pb(II), Zn(II), Ni(II), and Cr(III) are investigated by a batch technique. Based on the research results of binding capacity, adsorption isotherm, effect of pH value on sorption, and adsorption kinetics experiments, it is shown that the poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibers have higher binding capacities and good adsorption kinetic properties for heavy metal ions. The sorption of the metal ions on the chelating fibers is strongly dependent on the equilibrium pH value of the solution. The adsorption isotherms of Cu(II) and Cd(II) on the chelating fiber exhibit a Langmuir-type equation. The adsorbed Cu(II), Cd(II), Zn(II), and Pb(II) could be eluted by diluted nitric acid. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 7–14, 1998     

Flame atomic absorption spectrometric determination of Cd,Pb, and Cu in food samples after pre-concentration using 4-(2-thiazolylazo) resorcinol-modified activated carbon

This work aimed to develop a solid-phase extraction method using low-cost activated carbon produced from waste and modified with 4-(2-thiazolylazo) resorcinol for Cd(II), Pb(II), and Cu(II). The results showed that quantitative recovery of analytes was obtained at pH 6 with 3 M nitric acid as the eluent and a sample volume up to 1000 mL. The method was validated using certified reference material and addition-recovery tests. The limits of detection (LODs) for Pb(II), Cd(II), and Cu(II) were 2.03 μg L⁻¹, 0.15 μg L⁻¹, and 0.19 μg L⁻¹, respectively. The procedure was applied for determination of analytes in food samples.     

Activated carbon sorbent with thioetheric sites—preparation and characterization

An activated carbon sorbent containing thioetheric sites (ACTS) was prepared by modification of the activated carbon with 2,2′-thiodiethanol. The specific surface area, pore volume, concentration of oxygen-containing groups and sulfur content of the sorbent were determined. The sorption behavior towards ions of some precious metals—Au(III), Pt(IV), Pd(II) and heavy metals—Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II) was studied. Selectivity towards gold, palladium and platinum in the pH range 1–9 was observed. The capacity for gold was 80 mg g⁻¹. The sorption of Au(III) at pH 1 is not affected by milligram amounts of Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II). The sorbed gold species is Au(0).     

Heavy metals uptake from aqueous solutions and industrial wastewaters by humic acid-immobilized polymer/bentonite composite: Kinetics and equilibrium modeling

This study explored the feasibility of utilizing a novel adsorbent, humic acid-immobilized-amine-modified polyacrylamide/bentonite composite (HA-Am-PAA-B) for the adsorption of Cu(II), Zn(II) and Co(II) ions from aqueous solutions. The FTIR and XRD analyses were done to characterize the adsorbent material. The effects of pH, contact time, initial adsorbate concentration, ionic strength and adsorbent dose on adsorption of metal ions were investigated using batch adsorption experiments. The optimum pH for Cu(II), Zn(II) and Co(II) adsorption was observed at 5.0, 9.0 and 8.0, respectively. The mechanism for the removal of metal ions by HA-Am-PAA-B was based on ion exchange and complexation reactions. Metal removal by HA-Am-PAA-B followed a pseudo-second-order kinetics and equilibrium was achieved within 120 min. The suitability of Langmuir, Freundlich and Dubinin-Radushkevich adsorption models to the equilibrium data was investigated. The adsorption was well described by the Langmuir isotherm model. The maximum monolayer adsorption capacity was 106.2, 96.1 and 52.9 mg g^?1 for Cu(II), Zn(II) and Co(II) ions, respectively, at 30 °C. The efficiency of HA-Am-PAA-B in removing metal ions from different industry wastewaters was tested. Adsorbed metal ions were desorbed effectively (97.7 for Cu(II), 98.5 for Zn(II) and 99.2% for Co(II)) by 0.1 M HCl. The reusability of the HA-Am-PAA-B for several cycles was also demonstrated.     

Mercury(II) removal from aqueous solution by sorption onto alginate,pectate and polygalacturonate calcium gel beads. A kinetic and speciation based equilibrium study

Gel beads of calcium alginate, pectate and polygalacturonate salts have been tested as sorbent materials for mercury(II) removal from aqueous solutions. Physico-chemical properties of gel beads, defined by SEM–EDX, TGA and texture and density analysis, were correlated with gel beads sorption capacity towards Hg²⁺ ion. A speciation study in aqueous solution was carried out to define the strength of interaction of mercury ion with the polymers investigated and to assess the more suitable experimental conditions to achieve the best effectiveness of Hg²⁺ sorption by gel beads. On the basis of the speciation study, pH values in the 3–5.5 pH range were considered appropriated for mercury(II) sorption by gel beads. Kinetics of mercury(II) sorption and calcium(II) release from the sorbent materials were studied at pH 3, 3.6 and 5.2. The highest sorption rate (K) and amount of mercury(II) adsorbed were obtained at pH 3 and 3.6; therefore, pH 3.3 was chosen for the equilibrium study of Hg²⁺ sorption at 25 °C. The results obtained by using Langmuir and Freundlich isotherm equations show the following sorption capacity trend: Ca–Pect > Ca–PGA > Ca–AA.     

Polyacrylate anion exchangers in sorption of heavy metal ions with non-biodegradable complexing agents

The polyacrylate anion exchangers are widely used in purification of heavy metal ions from wastewaters and different accompanying complexing agents. Such effluents containing the chelators (EDTA, NTA, HEDTA, DTPA, and IDA) are discharged from relevant industries such as printed circuits boards, plating on plastics, metal finishing and others. The sorption was studied as a function of phase contact time and pH by the batch technique. It was found that the removal of heavy metal ions in the presence of EDTA, NTA and IDA strictly depends on the phase contact time and pH values. Various kinetic models such as the pseudo first-order and the pseudo second-order as well as the intraparticle one were also tested to estimate the sorption rate. The equilibrium capacities of the studied anion exchangers for Cu(II), Zn(II), Co(II), Ni(II), Pb(II) and Cd(II) in the presence of EDTA were the highest for Pb(II) and Cd(II). The order of sorption for Amberlite IRA 458, Amberlite IRA 958 as well as Amberlite IRA 67 can be as follows: Pb(II) > Cd(II) > Zn(II) > Cu(II) > Ni(II) > Co(II). The stability of forming complexes was also compared. The estimation of the capacities of anion exchangers under investigation by the continuous column studies was also carried out.     

High surface area-activated carbon from Glycyrrhiza glabra residue by ZnCl2 activation for removal of Pb(II) and Ni(II) from water samples

A high-surface-area activated carbon was prepared by chemical activation of Glycyrrhiza glabra residue with ZnCl₂ as active agent. Then, the adsorption behavior of Pb(II) and Ni(II) ion onto produced activated carbon has been studied. The experimental data were fitted to various isotherm models. According to Langmuir model, the maximum adsorption capacity of Pb(II) and Ni(II) ions were found to be 200 and 166.7 mg g⁻¹, respectively, at room temperature. Kinetic studies showed the adsorption process followed pseudo second-order rate model. High values of intra-particle rate constants calculated shows the high tendency of activated carbon for removal of Pb(II) and Ni(II) ions.     

Sorption studies of manganese and cobalt from aqueous phase onto alginate beads and nano-graphite encapsulated alginate beads

Comparative sorption study of dissolved manganese and cobalt ions onto alginate beads (ABs) and thermally activated nano-carbon beads (NCBs) was performed. Acidic functionalities dominate over sorbent surface. Elemental analysis confirmed that divalent calcium replacement with heavy metal ions might be a possible sorption mechanism. Optimum metal uptake was observed at pH 8. Most of the metal ions (80–92%) were sorbed within 4 h, followed by a slower sorption stage. Mn(II) and Co(II) recovery was greater than 99% with 0.1 N HCl, and NCB could be repeatedly utilized for Mn(II) and Co(II) sorption with negligible loss in sorption capacity.     

Synthesis,characterization and application of a chelating resin for solid phase extraction of some trace metal ions from water,sediment and tea samples

A new chelating resin, poly (2-thiozylmethacrylamide-co-divinylbenzene -co-2-acrylamido-2-methyl-1-propanesulfonic acid) was successfully prepared in the present work. Its composition, morphology, and properties were studied by Fourier transform infrared spectroscopy, scanning electron microscopy, elemental analysis, and thermogravimetric analysis. Several factors affecting the extraction of the metal ions including pH, the eluent type and concentration, flow rate, sample volume, and effect of interfering ions were investigated. The adsorption capacity of the resin for the elements studied was found in the range of 4.76–13.0 mg g⁻¹. A preconcentration factor of 150 was achieved at the optimum conditions. The limits of detection (3s/b) varied from 0.23 to 1.07 μg L⁻¹. The method validation was performed by analyzing certified reference materials (TMDA-70 Fortified lake water, SPS-WW1 Batch 111-Wastewater, RM 8704 Buffalo river sediment, GBW07605 Tea) and spiked water samples. The method was applied to separate and determine the trace levels of Cd(II), Ni(II), Co(II), Mn(II) and Pb(II) in the well water, river water, street sediment, and tea samples.     

One-step preparation of Pt–M@FP-MWNT catalysts (M = Ru,Ni, Co,Sn, and Au) by γ-ray irradiation and their catalytic efficiency for CO and MeOH

Pt–M@FP-MWNT catalysts (M = Ru, Ni, Co, Sn, and Au) were prepared by one-step γ-ray irradiation. Two different types of functional polymers (FP), such as poly(vinylphenyl boronic acid) (PVPBAc) and poly(vinylpyrorridone) (PVP), were used as anchoring agents, when Pt–M nanoparticles were deposited on the multi-walled carbon nanotube (MWNT) using γ-ray irradiation in aqueous solution at room temperature. The obtained Pt–M@FP-MWNT catalysts were then characterized by XRD, TEM, and elemental analysis. The catalytic efficiency of the Pt–M@FP-MWNT catalysts was examined for CO stripping and MeOH oxidation for use in a direct methanol fuel cell (DMFC). The catalytic efficiency of the Pt–M@FP-MWNT catalyst for MeOH oxidation follows this order: Pt–Sn@FP-MWNT > Pt–Co@FP-MWNT > Pt–Ru@FP-MWNT > Pt–Au@FP-MWNT > Pt–Ni@FP-MWNT catalysts. The CO adsorption capacity of the Pt–M@FP-MWNT catalyst for CO stripping is as follows: Pt–Ru@FP-MWNT > Pt–Sn@FP-MWNT > Pt–Au@FP-MWNT > Pt–Co@FP-MWNT > Pt–Ni@FP-MWNT catalyst.