Studies on two‐dimensional coordination polymer cadmium phosphate and its high efficient adsorption of Pb(II) ions from aqueous solutions

The two‐dimensional coordination polymer cadmium phosphate with the morphology of rectangle layers was prepared by solid‐state template reaction at room temperature, and was characterized by XRD, FTIR, and TEM techniques. The as‐synthesized sample is a layered cadmium phosphate material, in which the structure is poly (CdPO₄^?) anion framework with ammonium ions and water species residing in the space between the layers, and cadmium ions are coordinated by the phosphate oxygen atoms. This article also presents the adsorption of Pb(II) ions from aqueous solution on the as‐synthesized coordination polymer cadmium phosphate, and the results showed that this inorganic polymer adsorbent had good adsorption capacity. It could reach to the saturation adsorption capacity within an hour, and its excellent adsorption capacity for Pb(II) was 5.50 mmol/g when the initial solution concentration was 1.68 × 10³ μg/mL at T = 278K. Moreover, the adsorption kinetics and adsorption isotherms were studied, it revealed that the adsorption kinetics can be modeled by pseudo second‐order rate equation wonderfully. The apparent activation energy (E_a), ΔG, ΔH, and ΔS were 3.16 kJ mol^?1, ?13.97 kJ mol^?1, ?11.84 kJ mol^?1, and 7.66 J mol^?1 K^?1, respectively. And it was found that Langmuir equation could well interpret the adsorption of the as‐synthesized coordination polymer cadmium phosphate for Pb(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of temperature on the removal of lead(II) by adsorption on China clay and wollastonite

The removal of Pb(II) from aqueous solution by adsorption on china clay and wollastonite is an attractive process. The amount of Pb(II) removed by adsorption is highly dependent on the temperature of the adsorbate solution and favours low temperature. The equilibrium times were noted, i.e. 90 min for china clay and 120 min for wollastonite. The various rate parameters of the adsorption process have been determined at different temperatures. The activation energies were determined and found to be ?5.345 kJ mol^?1 and ?8.730 kJ mol^?1 for Pb(II)-china clay and Pb(II)-wollastonite systems, respectively. The adsorption isotherm was measured experimentally at various temperatures. The negative values of enthalpy change (ΔH = ?77.95 kJ mol^?1 and ?16.40 kJ mol^?1 for china clay and wollastonite, respectively) indicate the exothermic nature of the adsorption processes for both systems. The isosteric heats of the adsorption process have been determined at various surface coverages of the adsorbents used. The various thermodynamic parameters have been calculated to elucidate the mechanism involved in the adsorption process.     

Removal of Pb(II) from aqueous solutions by adsorption onto clayey soil of Indian origin: Equilibrium, kinetic and thermodynamic profile

The feasibility of applying natural, untreated clayey soil as low-cost alternative adsorbent for Pb(II) removal from aqueous solutions was investigated with a batch experimental set-up. Experiments were carried out as a function of initial solution pH (1?C8), contact time (10?C360 min), initial Pb(II) concentration (20?C100 mg L^?1), adsorbent dose (0.5?C5 g) and temperature (303?C333 K). Adsorption equilibrium data were well described by the Langmuir isotherm with maximum adsorption capacity of 121.86 mg g^?1 at 303 K. Adsorption of Pb(II) followed pseudo-second-order kinetics. Gibbs free energy (??G⁰) was spontaneous for all interactions, and the adsorption process exhibited exothermic enthalpy values. The adsorbent was easily regenerated by using 0.1M HNO₃ solution and was reused for five sorptiondesorption cycles without any considerable loss in adsorption capacity. It could be concluded that clayey soil may be used as an inexpensive and effective adsorbent without any treatment or any other modification for the removal of Pb(II) ions from aqueous solutions.     

Kinetic and thermodynamic investigation of Arthrospira (Spirulina) platensis fed‐batch cultivation in a tubular photobioreactor using urea as nitrogen source

BACKGROUND: Fed‐batch culture allows the cultivation of Arthrospira platensis using urea as nitrogen source. Tubular photobioreactors substantially increase cell growth, but the successful use of this cheap nitrogen source requires a knowledge of the kinetic and thermodynamic parameters of the process. This work aims at identifying the effect of two independent variables, temperature (T) and urea daily molar flow‐rate (U), on cell growth, biomass composition and thermodynamic parameters involved in this photosynthetic cultivation. RESULTS: The optimal values obtained were T = 32 °C and U = 1.16 mmol L^?1 d^?1, under which the maximum cell concentration was 4186 ± 39 mg L^?1, cell productivity 541 ± 5 mg L^?1 d^?1 and yield of biomass on nitrogen 14.3 ± 0.1 mg mg^?1. Applying an Arrhenius‐type approach, the thermodynamic parameters of growth (ΔH* = 98.2 kJ mol^?1; ΔS* = ? 0.020 kJ mol^?1 K^?1; ΔG* = 104.1 kJ mol^?1) and its thermal inactivation ( kJ mol^?1; kJ mol^?1 K^?1; kJ mol^?1) were estimated. CONCLUSIONS: To maximize cell growth T and U were simultaneously optimized. Biomass lipid content was not influenced by the experimental conditions, while protein content was dependent on both independent variables. Using urea as nitrogen source prevented the inhibitory effect already observed with ammonium salts. Copyright © 2012 Society of Chemical Industry     

Adsorption of lead(II) from aqueous solution by activated carbon prepared from Eichhornia

Activated carbon prepared from Eichhornia was used for the adsorptive removal of Pb(II) from aqueous solution. As the raw material for the preparation of the activated carbon is an aquatic weed, the production of this carbon is expected to be economically feasible. Parameters such as agitation time, metal ion concentration, adsorbent dose and pH were studied. Adsorption equilibrium was reached in 100 min for a solution containing 15 mgdm^?3 and 125 min for solutions containing 20 and 25 mgdm^?3 Pb(II), respectively. Adsorption parameters were determined using both Langmuir and Freundlich isotherm models. The adsorption capacity was 16.61 mgg^?1 at pH 3.0 for particle sizes of 125–180 µm. Pb(II) removal increased as the pH increased from 2 to 4 and remained constant up to pH 10.0. Desorption studies were also carried out with dilute hydrochloric acid to recover both carbon and Pb(II). Quantitative desorption of Pb(II) from carbon indicates that adsorption of metal ion is by ion exchange. © 2002 Society of Chemical Industry     

Synthesis,characterization, and application of a new chelating resin functionalized with dithiooxamide

Chloromethylated polystyrene‐divinylbenzene has been functionalized with dithiooxamide. The resulting chelating resin (DTOA) has been characterized by elemental analyses, infrared spectroscopy, thermogravimetric analysis, and metal ion sorption capacities. It has been used for the preconcentration and separation of Cu(II), Zn(II), Cd(II), and Pb(II) prior to their determination by FAAS. Parameters such as the amount of the resin, effect of pH, equilibration rate, sorption and desorption of metal ions, and effect of diverse ions have been studied. The maximum sorption capacities found are 0.97, 0.12, 0.08, and 0.12 mmol g^?1 for Cu(II), Zn(II), Cd(II), and Pb(II) at pH 6.0, 5.5, 1.0, and 5.5, respectively. The preconcentration factors are 100, 100, 50, and 50 for Cu(II), Zn(II), Cd(II), and Pb(II), respectively. Recoveries of the metal ions were 96 ± 5, 97 ± 6, 96 ± 5, and 96 ± 5 at 95% confidence level, whereas the limits of detection are 2.0, 1.3, 2.5, and 25.0 μg L^?1 for Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The calibration curves were linear up to 12 μg mL^?1 (R² = 1.000), 2 μg mL^?1 (R² = 0.998), 2 μg ml^?1 (R² = 1.000), and 5 μg mL^?1 (R² = 0.979) for Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The reliability of the method has been tested by analyzing certified samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2281–2285, 2007     

Self-assembly of thiourea intercalated graphene oxide based dual IIP for the SPE coupled FAAS method development of Cu(II) and Pb(II) determination

A new dual-template surface imprinted polymer for Cu(II) and Pb(II) was synthesized in one pot. Magnetic graphene oxide was self-assembled with low cost and environmentally benign thiourea. Presence of sulfur and nitrogen donor atoms provide hooks for coordination and partial reduction of graphene oxide matrix. It was used as an solid-phase extraction adsorbent for extraction, preconcentration, and coupled with flame atomic absorption spectrometry to manifest performance comparable with inductively coupled plasma atomic emission spectrometry (ICPAES) both in terms of quantification limit as well as interference. The critical experimental parameters such as pH; 4.6, contact time of 15 min and initial concentration of 777 (Q_e; 227 mg g⁻¹) and 800 μg L⁻¹ (Q_e; 273 mg g⁻¹) for Cu(II) and Pb(II), respectively, were optimized using RSM-CCD and artificial neural network. The adsorption process was kinetically faster (50% adsorption in 5 min), following fractal-like-pseudo-second-order (FLPSO) kinetics and Brouers–Sotolongo isotherm model owing to the heterogenous energy landscape. The imprinting factors were in the range of 4–7 in the presence of all coexisting ions. The proposed method was robust in the determination and removal of Cu(II) and Pb(II) from food, ground water, and industry effluents with low limit of detection (Cu(II); 1.03 μg L⁻¹ & Pb(II); 1.79 μgL⁻¹). Spiking and recovery tests were used to assess the method's accuracy. Cu(II)/Pb(II) loaded dual template IIP (DIIP) was utilized to remove anionic dyes with >95% efficiency. Thorough examination of the method and material selectivity (in binary, ternary, and multielement system), multi fold applications of determination, removal of Cu(II), Pb(II), and removal of anionic dyes makes DIIP a promising candidate for environmental remediation.     

Synthesis of novel silica-gel-supported thiosemicarbazide and its properties for solid phase extraction of mercury

A new thiosemicarbazidе-modi?ed silica gel (SG-THSC) sorbent was prepared. The sorbent was quantified by adsorption of mercury ions on silica gel, desorption and then spectrophotometry detection of mercury ions. The retention parameters (sample flow rate, eluent type, sample volume, presence of foreign ions, shaking time, sample flow rate and volume, eluent condition, interfering substances) were investigated. The quantitative recovery (>95%) of Hg(II) ions could be obtained by use of 5 mL of 6 mol L^?1 HCl. The adsorption capacity of SG-THSC was found to be 98.3 mg g^–1 at optimum pH. The maximum preconcentration factor was 400. The technique detection limit was 70 ng L^–1, and the relative standard deviation was lower than 4.0% (n = 6). The studied sorbent was applied to preconcentrate the trace Hg(II) from the mineralised residues of fish and seawater samples.     

Optimization of Cu(II)-ion imprinted nanoparticles for trace monitoring of copper in water and fish samples using a Box–Behnken design

We describe a nanoparticles ion-imprinted polymer (IIP) for the selective preconcentration of copper (II) ions. It was obtained by precipitation polymerization from 2-vinylpyridine (the functional monomer), ethylene glycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the initiator), 2,9-dimethyl-1,10-phenanthroline (the copper-binding ligand) and nickel nitrate (the template ion) in acetonitrile solution. The IIP particles were characterized by Fourier Transformed Infra Red Spectroscopy (FTIR), thermogravimetric and differential thermal analysis, and by scanning electron microscopy. The optimization process was carried out using the Box–Behnken design (BBD). Effects of several factors such as solution pH for adsorption, amount of polymer, type, concentration and volume of eluent for extraction, as well as adsorption and desorption times were investigated. Under the optimum conditions (type and concentration of eluent, HCl 1.6 mol L^?1; volume of eluent, 6 mL; adsorption solution pH, 6.0; amount of polymer, 30 mg; adsorption time, 25 min; desorption time, 25 min), preconcentration factor of the proposed method was approximately 100. Under the optimized conditions, the detection limit was found to be 0.1 μg L^?1, while the relative standard deviation (RSD) for six replicate measurements was calculated to be <4%.     

Biosorption of Pb(II) and Ni(II) ions by chemically modified Eclipta alba stem powder: Kinetics and equilibrium studies

Biosorption of Pb(II) and Ni(II) ions onto the Eclipta alba stem powder (EAS) was investigated in a batch system. The biosorbent was characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), transmission electron microscopy (TEM) and elemental analysis. Adsorption influencing factors like pH, adsorbent dose, initial metal ion concentration and contact time were investigated. The adsorption mechanism of Pb(II) and Ni(II) followed the pseudo-second-order kinetic model (R² > 0.998). The Langmuir isotherm model fitted well and the maximum monolayer adsorption capacity of the sorbent for Pb(II) and Ni(II) was found to be 66.2 ± 1.9 mg g^?1and 62.5 ± 1.8 mg g^?1, respectively. Desorption and recovery were carried out using dilute HCl solution.     

Syntheses and adsorption properties for Hg2+ of chelating resin of crosslinked polystyrene‐supported 2,5‐dimercapto‐1,3,4‐thiodiazole

A novel chelating resin with functional group containing S and N atoms was prepared using chloromethylated polystyrene and 2,5‐dimercapto‐1,3,4‐thiodiazole (also called bismuththiol I, BMT) as materials. Its structure was characterized by infrared spectra and elementary analysis. The results showed that the content of the functional group was 2.07 mmol BMT g^?1 resin, 47% of which were in the form of monosubstitution (PS‐BMT‐1) and 53% in the form of double substitution (PS‐BMT‐2). The adsorption for mercury ion was investigated. The adsorption dynamics showed that the adsorption was controlled by liquid film diffusion. Increasing the temperature was beneficial to adsorption. The Langmuir model was much better than the Freundlich model to describe the isothermal process. The adsorption activation energy (E_a), ΔG, ΔH, and ΔS values calculated were 18.56 kJ·mol^?1, ‐5.99 kJ·mol^?1, 16.38 kJ·mol^?1, and 37.36, J·mol^?1·K^?1, respectively. The chelating resin could be easily regenerated by 2% thiourea in 0.1 mol·L^?1 HCl with higher effectiveness. Five adsorption–desorption cycles demonstrated that this resin was suitable for repeated use without considerable change in adsorption capacity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1646–1652, 2004     

Pyromellitic dianhydride‐modified β‐cyclodextrin microspheres for Pb(II) and Cd(II) adsorption

In this work, the pyromellitic dianhydride (PMDA)‐grafted β‐cyclodextrin (β‐CD) microspheres have been prepared for the removal of lead and cadmium metal ions in aqueous solution by a batch‐equilibration technique. The effects of the pH of the solution, contact time, and initial metal concentration were studied. The adsorption capacities for the two metal ions increase significantly as a large number of carboxyl groups are present on the microspheres surface. The equilibrium process is better described by the Langmuir isotherm than the Freundlich isotherm. The maximum adsorption capacities are 135.69 and 92.85 mg g^?1 for Pb(II) and Cd(II), respectively. Kinetic studies show good correlation coefficients for a pseudosecond‐order kinetic model, confirming that the sorption rate is controlled by chemical adsorption. The regeneration of the adsorbent can be carried out by treating the loaded microspheres with 0.2 (mol L^?1) HCl obtaining high desorption rate for the two metal ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Treatment of paper and pulp wastewater and removal of odorous compounds by a Fenton‐like process at the pilot scale

A Fenton‐like process, involving oxidation and coagulation, was evaluated for the removal of odorous compounds and treatment of a pulp and paper wastewater. The main parameters that govern the complex reactive system [pH and Fe(III) and hydrogen peroxide concentrations] were studied. Concentrations of Fe(III) between 100 and 1000 mg L^?1 and of H₂O₂ between 0 and 2000 mg L^?1 were chosen. The main mechanism for color removal was coagulation. The maximum COD, color and aromatic compound removals were 75, 98 and 95%, respectively, under optimal operating conditions ([Fe(III)] = 400 mg L^?1; [H₂O₂] = 500–1000 mg L^?1; pH = 2.5; followed by coagulation at pH 5.0). The biodegradability of the wastewater treated increased from 0.4 to 0.7 under optimal conditions and no residual hydrogen peroxide was found after treatment. However, partially or non‐oxidized compounds present in the treated wastewater presented higher acute toxicity to Artemia salina than the untreated wastewater. Based on the optimum conditions, pilot‐scale experiments were conducted and revealed a high efficiency in relation to the mineralization of organic compounds. Terpenes [(1S)‐α‐pinene, β‐pinene, (1R)‐α‐pinene and limonene] were identified in the wastewater and were completely eliminated by the Fenton‐like treatment. Copyright © 2006 Society of Chemical Industry     

Batch and fixed‐bed column adsorption of Cu(II), Pb(II) and Cd(II) from aqueous solution onto functionalised SBA‐15 mesoporous silica

Functionalised SBA‐15 mesoporous silica with polyamidoamine groups (PAMAM‐SBA‐15) was successfully prepared with the structure characterised by X‐ray diffraction, nitrogen adsorption–desorption, Fourier transform infrared spectra and thermogravimetric analysis. PAMAM‐SBA‐15 was applied as adsorbent for Cu(II), Pb(II) and Cd(II) ions removal from aqueous solution. The effects of the solution pH, adsorbent dosage and metal ion concentration were studied under the batch mode. The Langmuir model was fitted favourably to the experimental data. The maximum sorptive capacities were determined to be 1.74 mmol g^?1 for Cu(II), 1.16 mmol g^?1 for Pb(II) and 0.97 mmol g^?1 for Cd(II). The overall sorption process was fast and its kinetics was fitted well to a pseudo‐first‐order kinetic model. The mean free energy of sorption, calculated from the Dubinin–Radushkevich isotherm, indicated that the sorption of lead and copper, with E > 16 kJ mol^?1, followed the sorption mechanism by particle diffusion. The adsorbent could be regenerated three times without significant varying its sorption capacity. A series of column tests were performed to determine the breakthrough curves with varying bed heights and flow rates. The breakthrough data gave a good fit to the Thomas model. Maximum sorption capacity of 1.6, 1.3 and 1.0 mmol g^?1 were found for Cu(II), Pb(II) and Cd(II), respectively, at flow rate of 0.4 mL min^?1 and bed height of 8 cm, which corresponds to 83%, 75% and 73% of metallic ion removal, respectively, which very close to the value determined in the batch process. Bed depth service time model could describe the breakthrough data from the column experiments properly. © 2012 Canadian Society for Chemical Engineering     

Biosorption of Strontium Ions by Magnetically Modified Yeast Cells

The sorption of Sr²⁺ ions from aqueous solutions on magnetically modified fodder yeast (Kluyveromyces fragilis) cells and their subsequent desorption were studied. The Sr²⁺ sorption increased with increasing pH and reached a plateau between pH 4.0 and 7.0. The changes of temperature slightly influenced the sorption process. The sorption values were 19.5 mg g^?1 and 53.5 mg g^?1 for 10 mg L^?1 and 40 mg L^?1 Sr²⁺ solutions respectively after 20 min incubation at a pH higher than 4. The Langmuir isotherm was successfully used to fit experimental data; the maximum adsorption capacity was 140.8 mg g^?1 under optimal conditions. The adsorbed Sr²⁺ ions can be desorbed with nitric acid (0.1 mol L^?1).     

Biosorption of Pb(II) ions from aqueous solution by pine bark (Pinus brutia Ten.)

The biosorption potential of pine (Pinus brutia Ten.) bark in a batch system for the removal of Pb(II) ions from aqueous solutions was investigated. The biosorption characteristics of Pb(II) ions on the pine bark was investigated with respect to well-established effective parameters including the effects of solution pH, initial Pb(II) concentration, mass of bark, temperature, and interfering ions present, reusability, and desorption. Initial solution pH and contact time were optimized to 4.0 and 4 h, respectively. The Langmuir and Freundlich equilibrium adsorption models were studied and observed to fit well. The maximum adsorption capacity of the bark for Pb(II) was found to be 76.8 mg g⁻¹ by Langmuir isotherms (mass of bark: 1.0 g L⁻¹). The kinetic data fitted the pseudo-second-order model with correlation coefficient greater than 0.99. The thermodynamic parameters Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were also calculated, and the values indicated that the biosorption process was spontaneous. Reutilization of the biosorbent was feasible with a 90.7% desorption efficiency using 0.5 M HCl. It was concluded that pine bark can be used as an effective, low cost, and environmentally friendly biosorbent for the removal of Pb(II) ions from aqueous solution.     

Behaviour and mechanism of enhanced phosphate sorption on loess modified with metals: equilibrium study

BACKGROUND: Phosphate is one of the main contaminants responsible for the eutrophication of surface waters. In developing countries, algae blooming in lakes have threatened the quality of drinking water due to the lack of proper management of phosphate‐containing wastewaters from mining sites and industry. MAJOR RESULTS: The sorption behaviour of phosphate on loess modified by metals (Zn(II), Cu(II) and Pb(II)) was investigated in this paper. Zn(II) and Cu(II) sorption on the loess was attributed to the constituent silicate minerals while the sorption of Pb(II) was assigned to natural carbonate in the loess. The sorption affinity of phosphate towards the modified sorbent was as follows: Pb(II) (221.3–832.2 L g⁻¹) > Cu(II) (20.26 L g⁻¹) > Zn(II) (0.77–1.90 L g⁻¹) > loess (0.11 L g⁻¹) with regard to the partition coefficient. The sorption isotherms were well fitted by an extended Henry's law with multi‐linearity. Several factors including metal loading, pH, sorbent dosage and temperature were investigated and all were found to correlate positively with phosphate sorption. The enthalpy and entropy changes during phosphate sorption on Pb(II) loaded loess were predicted as 14.32 kJ mol⁻¹ and 128.45 J mol⁻¹ K⁻¹, respectively. The sorption mechanism for phosphate on Pb(II) doped loess was investigated by FT‐IR spectra from which the sorption was attributed to chemical bonding with lead carbonate and physisorption with surface adsorbed phosphate as well as diffusion through micropores into the sorbent. CONCLUSIONS: Pb(II) loaded loess shows the best performance for phosphate removal from aqueous solution. The optimum conditions for sorption were pH = 9.5, lead modified loess sorbent dosage = 10 g L⁻¹, temperature = 35 °C and Pb(II) loading 295 mg g⁻¹. Copyright © 2008 Society of Chemical Industry     

Paddle cactus (Tacinga palmadora) as potential low-cost adsorbent to treat textile effluents containing crystal violet

Abstract

The powdered biomass of paddle cactus (Tacinga palmadora), a rustic plant of great occurrence in the driest regions of Brazil, was evaluated as a low-cost adsorbent to treat textile effluents containing crystal violet (CV) dye. The powdered paddle cactus (PPC) was mainly composed by lignin and holocellulose, as well as, a variety of functional groups. Best results for CV adsorption were found using an adsorbent dosage of 0.5?g L^?1 at solution pH equivalent to 10.0. Fast adsorption kinetics was verified, being the equilibrium reached within 100?min, and the curves were well modeled by the pseudo-first-order model. The isotherms were well-represented by the Langmuir model. The maximum adsorption capacity was 228.74?mg g^?1 at 328?K. The estimated thermodynamics parameters were ΔG⁰_T?=?328K of –9.08?kJ mol^?1, ΔH⁰ of 12.44?kJ mol^?1, and ΔS⁰ of 0.065?kJ mol^?1 K^?1. In addition, PPC was able to treat a simulated textile effluent containing organic and inorganic compounds, reaching 93% of color removal efficiency. These findings show that powdered paddle cactus can be applied as potential low-cost adsorbent to treat textile effluents containing CV.     

Adsorption of BTX compounds from aqueous solutions by water-insoluble starch

The removal of benzene, toluene and p-xylene (BTX) compounds from aqueous solutions with highly crosslinked cationic starch containing tertiary amine groups was investigated. The adsorption process has found to be initial pH- and initial concentration-dependent, endothermic, and follows the Langmuir isothermal adsorption. The heats of adsorption (ΔH) at initial pH = 4 of benzene, toluene and p-xylene compounds are 29.45 kJ mol^?1, 34.41 kJ mol^?1, and 35.58 kJ mol^?1, respectively, those at initial pH = 10 are 30.17 kJ mol^?1, 35.56 kJ mol^?1, and 39.39 kJ mol^?1, respectively. The order of the amount of adsorbed BTX compounds on the adsorbent is benzene > toluene > p-xylene.