Sorption of nickel on chitosan

The sorption of nickel on chitosan was studied using batch method. As a tracer was used radioisotope ⁶³Ni. The effect of pH and contact time to reach sorption equilibrium was investigated. During the sorption of Ni²⁺ ions occur mostly to ion-exchange reactions on the surface of sorbent. The time to reach the sorption equilibrium of nickel on chitosan was 14 h. The percentage of sorption after 14 h achieved the value of 84 %. On the sorption of nickel used solutions with initial pH in the range from 3.9 to 8.1. In the monitored range of pH after 24 h of contact was the sorption of nickel on chitosan >97 %. The sorption of nickel was reduced by increasing concentrations of Ni²⁺ ions in the solution. The experimental data for sorption of nickel have been interpreted in the term of Langmuir isotherm and the value of maximum sorption capacity of nickel on chitosan was 2.71 × 10^?3 mol g^?1.     

Study of sorption processes of strontium on the synthetic hydroxyapatite

The sorption of strontium on synthetic hydroxyapatite was investigated using batch method and radiotracer technique. The hydroxyapatite samples were prepared by a wet precipitation process followed by calcination of calcium phosphate that precipitated from aqueous solution. Also, commercial hydroxyapatites were used. The sorption of strontium on hydroxyapatite depended on the method of preparation and it was pH independent ranging from 4 to 9 as a result of buffering properties of hydroxyapatite. The distribution coefficient K _d was significantly decreased with increasing concentration of Sr²⁺ and Ca²⁺ ions in solution with concentration above 1 × 10⁻³ mol dm⁻³. The percentage strontium sorption for commercial and by wet method prepared hydroxyapatite was in the range of 83–96%, while calcined hydroxyapatite was ranging from 10 to 30%. The experimental data for sorption of strontium have been interpreted in the term of Langmuir isotherm. The sorption of Sr²⁺ ions was performed by ion-exchange with Ca²⁺ cations on the crystal surface of hydroxyapatite. Although calcined hydroxyapatite is successfully used as biomaterial for hard tissues repair, it is not used for the treatment of liquid wastes.     

Distribution of strontium in milk component

The distribution of strontium between the milk components, i.e., serum, casein micelles, whey and hydroxyapatite was determined. The sorption on hydroxyapatite was investigated using batch method and radiotracer technique. The aqueous phase comprised of either milk or whey. The sorption of strontium on hydroxyapatite depended on the method of its preparation and on the composition of the aqueous phase. The sorption of strontium was increased with an increase of pH. The presence of citrate species resulted in decrease of the sorption of strontium on hydroxyapatite. The sorption of ⁸⁵Sr on hydroxyapatite decreased with the increasing concentration of Ca²⁺ ions. Addition of Ca²⁺ ions to milk resulted in milk pH decrease. The decrease in pH value after calcium addition to milk is related to exchanges between added calcium and micellar H⁺. The average value of strontium sorption on casein micelles in milk with presence of hydroxyapatite was (47.3 ± 5.6) %. The average value of sorption of ⁸⁵Sr on casein micelles in milk without the addition of hydroxyapatite was (68.9 ± 2.2) %.     

Ultrasensitive Detection of Cu<Superscript>2+</Superscript> Using a Microcantilever Sensor Modified with L-Cysteine Self-Assembled Monolayer

A microcantilever was modified with a self-assembled monolayer (SAM) of L-cysteine for the sensitively and selectively response to Cu(II) ions in aqueous solution. The microcantilever undergoes bending due to sorption of Cu(II) ions. The interaction of Cu(II) ions with the L-cysteine on the cantilever is diffusion controlled and does not follow a simple Langmuir adsorption model. A concentration of 10^?10 M Cu(II) was detected in a fluid cell using this technology. Other cations, such as Ni²⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, K⁺, and Na⁺, did not respond with a significant deflection, indicating that this L-cysteine-modified cantilever responded selectively and sensitively to Cu(II).     

Separation of Ni<Superscript>2+</Superscript> from ammonia solution through a supported liquid membrane impregnated with Acorga M5640

Separation of Ni²⁺ from ammonia/ammonium chloride solution using a flat-sheet supported liquid membrane (SLM) impregnated with Acorga M5640 in kerosene was investigated. The fundamental experimental variables influencing Ni²⁺ transport, such as ammonia concentration, carrier concentration, H₂SO₄ concentration in the stripping solution, stirring speed, and initial Ni²⁺ concentration were studied. Almost all of Ni²⁺ was transported from the feed to the stripping phase after 18 h of operation with a permeability coefficient of 9.28 × 10^?6 m s^?1 under optimum conditions: stirring speed of 1000 rpm in both phases, 20 vol.% Acorga M5640 as the carrier, 1.70 mmol L^?1 Ni²⁺ in the feed phase and 0.10 mol L^?1 H₂SO₄ in the stripping phase. The flux value of Ni²⁺ was 15.82 × 10^?6 mol m^?2 s^?1. Additionally, the influences of temperature and ultrasound on flux were examined, and results indicated that higher temperature and ultrasonic assistance improved transport of Ni²⁺ through the SLM. Selective separation of nickel from cobalt in an ammonia/ammonium chloride solution was also achieved through SLM. The stability of the SLM was examined on a continuous run mode and satisfactory stability of the nickel permeation was observed for 84 h (7 runs).     

Polymer modified biomass of baker's yeast for treating simulated wastewater containing nickel and lead

Baker's yeast was cross‐linked by glutaraldehyde and then modified by grafting with poly(amic acid), which was prepared via reaction of pyromellitic dianhydride (PMDA) and arginine at 50°C. The morphology of the pristine, cross‐linked, and modified biomass was observed by microscope. The presence of poly(amic acid) on the biomass surface was verified by X‐ray photoelectron spectroscopy (XPS) analyses. Due to the high density of the functional groups on the modified biomass surface, the metal adsorption capacity for nickel and lead increased significantly, especially when the carboxylic acid groups were converted into carboxylate ions using NaOH. The adsorption process for nickel and lead adsorption followed the pseudo‐second‐order kinetics. The metal adsorption data were fitted with the Langmuir and Freundlich isotherms with the former having a better fit. Using the Langmuir adsorption isotherm, the maximum uptakes for nickel and lead were found to be 0.848 and 0.980 mmol g^?1 respectively which were about 15 and 11 times higher than the prisitine biomass. In the simulated wastewater containing 0.400 mmol l^?1 of Ni²⁺ and Pb²⁺, the metal adsorption capacity of Ni²⁺ and Pb²⁺ reached 0.365 mmol l^?1 and 0.390 mmol l^?1, respectively. The metal ions loaded biomass was regenerated using Ethylene Diamine Tetraacetic Acid (EDTA) solution and used repeatedly over four cycles with little loss of uptake capacity. Copyright © 2007 John Wiley & Sons, Ltd.     

New Ni(II) Ion-Selective Electrode Based on the N-S Schiff Base Ligand as Neutral Carrier in PVC Matrix

Abstract

A nickel(II) [Ni(II)] ion-selective electrode was prepared by incorporating a new N-S Schiff base ligand, glyoxal-bis(S-benzyldithiocarbazate) (GBSB), as a neutral carrier into the PVC matrix. The proposed electrode exhibits an excellent near-Nernstian response for Ni²⁺ ions, ranging from 2.8 × 10^?7 to 1.0 × 10^?1 mol/L with a detection limit of 1.2 × 10^?7 mol/L and a slope of 31.9 ± 0.3 mV/dec in pH 4.0 nitrate buffer solution at 25°C. It has an appropriate response time and suitable reproducibility and can be used for at least 3 months. The operational pH range of the proposed electrode is 4.0–7.5. The response mechanism is discussed in view of the alternating current (AC) impedance technique. In addition, the electrode was successfully used as an indicator electrode in potentiometric titration of Ni²⁺ ion and in the direct determination of Ni²⁺ ion in milk power and chocolate samples.     

Sorption of aqueous palladium onto synthetic hydroxyapatite

The sorption of Pd(II) on hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) has been studied at 25 °C as a function of pH, in 0.01 M NaClO₄, and 0.01 and 0.025 M Ca(ClO₄)₂ aqueous background electrolytes and Pd(II) concentration (9.3 to 47 ??M), trying to minimize some types of reactions, such as solid dissolution of and metal precipitation. The radiotracer palladium, ¹⁰⁹Pd, obtained by neutron irradiation, has been used to calculate the palladium??s distribution coefficients K _d between aqueous and solid phase. A mathematical treatment of results has been made by ion-exchange theory in order to interpret palladium sorption onto treated solid. For this, we take into account the existence of active sites at the hydroxyapatite surface, and the aqueous solution chemistry of palladium as well as the effect of phosphate anions from solid dissolution. The results can be explained as evidence of sorption of the species PdOH⁺, and of a mixed hydroxo complex of Pd²⁺ like (XCaO^?)?CPdOH⁺·nH₂O fixed onto {??Ca?COH} surface sites of the hydroxyapatite.     

SBA-15/Metformin as a novel sorbent combined with surfactant-assisted dispersive liquid–liquid microextraction (SA-DLLME) for highly sensitive determination of Pb,Cd and Ni in food and environmental samples

This paper established a new, rapid and sensitive method for the ultra-trace determination of lead, cadmium and nickel in food and environmental samples preconcentrated by dispersive solid-phase extraction (DSPE) combined with surfactant-assisted dispersive liquid–liquid microextraction (SA-DLLME) prior to graphite furnace atomic absorption spectrometry. SBA-15/Met was synthesized and used as a new efficient sorbent for the extraction of metal ions in DSPE. It was characterized by TEM and TGA techniques. After DSPE step, stripped metal elements were complexed with dithizone, and then, the complexes were extracted into carbon tetrachloride by using SA-DLLME. A conventional nonionic surfactant, triton X-100 was used as a disperser agent. Under the optimized conditions, the limit of quantifications was found to be 2.5 ng L^?1 for Pb²⁺, Cd²⁺ and 5.0 ng L^?1 for Ni²⁺. The limits of detection were 1.5 ng L^?1 for Ni²⁺ and 0.75 ng L^?1 for Pb²⁺ and Cd²⁺, with enrichment factor of 1650. The optimized method exhibited a good precision level with relative standard deviations (RSDs%) values of 4.9, 5.2 and 5.0% for 1 μg L^?1 Pb²⁺, Cd²⁺ and Ni²⁺, respectively (n = 7). Application of the proposed method to the analysis of fish-certified reference material produced results that were in good agreement with the certified values.     

Complexation of Nickel Ions by Boric Acid or (Poly)borates

An experiment based on electrochemical reactions and pH monitoring was performed in which nickel ions were gradually formed by oxidation of a nickel metal electrode in a solution of boric acid. Based on the experimental results and aqueous speciation modeling, the evolution of pH showed the existence of significant nickel–boron complexation. A triborate nickel complex was postulated at high boric acid concentrations when polyborates are present, and the equilibrium constants were determined at 25, 50 and 70 °C. The calculated enthalpy and entropy at 25 °C for the formation of the complex from boric acid and Ni²⁺ ions are respectively equal to (65.6 ± 3.1) kJ·mol^?1 and (0.5 ± 11.1) J·K^?1·mol^?1. The results of this study suggest that complexation of nickel ions by borates can significantly enhance the solubility of nickel metal and nickel oxide depending on the concentration of boric acid and pH. First principles calculations were investigated and tend to show that the complex is thermodynamically stable and the nickel cation in solution should interact more strongly with the \( {\text{B}}_{3} {\text{O}}_{3} \left( {\text{OH}} \right)_{4}^{ - } \) than with boric acid.     

The diffusion of H+ and Ni2+ ions in an inorganic cation-exchange matrix

The kinetics of sorption on zirconium hydrophosphates with various water contents was studied. The self-diffusion coefficients of Ni²⁺ and H⁺ and the effective diffusion coefficients of Ni²⁺ ions corresponding to the exchange Ni²⁺ → H⁺ were determined. The self-diffusion coefficients of ions in samples with an 85% water content were as high as 4.17 × 10^?11 m²/s (Ni²⁺) and 5.06 × 10^?10 m²/s (H⁺). Water loss caused by drying the sorbents resulted in a decrease in the rate of ion exchange.     

Optimized solid phase extraction based on diethyldithiocarbamate-coated Fe3O4 magnetic nanoparticles followed by ICP-OES for determination of Cd(II) and Ni(II) in rice and water samples

In the present study, application of Fe₃O₄ magnetic nanoparticles (MNPs) coated with diethyldithiocarbamate as a solid-phase sorbent for extraction of trace amounts of cadmium (Cd²⁺) and nickel (Ni²⁺) ions by the aid of ultrasound was investigated. The analytes were determined by inductively coupled plasma-optical emission spectroscopy. Fe₃O₄ MNPs were prepared by solvothermal method and characterized with dynamic light scattering, scanning electron microscope and X-ray diffraction. Response surface methodology was used for optimization of the extraction process and modeling the data. The optimal conditions obtained were as follows: chelating agent, 1.2 g L^?1; pH, 6.13; sonication time, 13 min and Fe₃O₄ MNPs, 10.3 mg. The calibration curves were linear over the concentration range of 1–1,000 μg L^?1 for Cd²⁺ and 2.5–1,000 for Ni²⁺ with the determination coefficients (R ²) of 0.9997 and 0.9995, respectively. The limits of detection were 0.27 μg L^?1 for Cd²⁺ and 0.76 μg L^?1 for Ni²⁺. The relative standard deviations (n = 7, C = 200 μg L^?1) for determination of Cd²⁺ and Ni²⁺ were 2.0 and 2.7 %, respectively. The relative recoveries of the analytes from tap, river and lagoon waters and rice samples at the spiking level of 10 μg L^?1 were obtained in the range of 95–105 %.     

Synthesis of tapioca cellulose-based poly(hydroxamic acid) ligand for heavy metals removal from water

A graft copolymerization was performed using free radical initiating process to prepare the poly(methyl acrylate) grafted copolymer from the tapioca cellulose. The desired material is poly(hydroxamic acid) ligand, which is synthesized from poly(methyl acrylate) grafted cellulose using hydroximation reaction. The tapioca cellulose, grafted cellulose and poly(hydroxamic acid) ligand were characterized by Infrared Spectroscopy and Field Emission Scanning Electron Microscope. The adsorption capacity with copper was found to be good, 210 mg g^?1 with a faster adsorption rate (t_1/2 = 10.5 min). The adsorption capacities for other heavy metal ions were also found to be strong such as Fe³⁺, Cr³⁺, Co³⁺ and Ni²⁺ were 191, 182, 202 and 173 mg g^?1, respectively at pH 6. To predict the adsorption behavior, the heavy metal ions sorption onto ligand were well-fitted with the Langmuir isotherm model (R² > 0.99), which suggest that the cellulose-based adsorbent i.e., poly(hydroxamic acid) ligand surface is homogenous and monolayer. The reusability was checked by the sorption/desorption process for six cycles and the sorption and extraction efficiency in each cycle was determined. This new adsorbent can be reused in many cycles without any significant loss in its original removal performances.     

Electrocatalytic oxidation of methanol by ZSM-5 nanozeolite-modified carbon paste electrode in alkaline medium

Development of a novel modified electrode for electrocatalytic oxidation of methanol in order to decrease overvoltage is importance. In this paper, carbon paste electrode (CPE) was modified by ZSM-5 nanozeolite. The average diameter of used nanozeolite was 97 nm. Ni²⁺ ions were incorporated to the nanozeolite by immersion of the modified electrode in a 0.1 M nickel chloride solution. Then, electrochemical studies of this electrode were performed by using cyclic voltammetry(CV) in alkaline medium. This modified electrode was used as an anode for the electrocatalytic oxidation of methanol in 0.1 M of NaOH solution. The obtained data demonstrated that ZSM-5 nanozeolite at the surface of CPE improves catalytic efficiency of the dispersed nickel ions toward methanol oxidation. The values of electron transfer coefficient, charge-transfer rate constant, and the electrode surface coverage are obtained 0.61, 0.2342 s^?1, and 4.33 × 10^?8 mol cm^?2, respectively. Also, the mean value of catalytic rate constant between the methanol and redox sites of electrode and diffusion coefficient were found to be 2.54 × 10⁴ cm³ mol^?1 s^?1 and 1.85 × 10^?8 cm² s^?1, respectively. Obtained results from both CV and chronoamperometric techniques indicated that the electrode reaction is a diffusion-controlled process.     

Stability and Detergent Compatibility of a Predominantly β-Sheet Serine Protease from Halotolerant B. aquimaris VITP4 Strain

The present study deals with the characterization of halotolerant protease produced by Bacillus aquimaris VITP4 strain isolated from Kumta coast, Karnataka, India. The studies were performed at 40 °C and pH 8 in Tris buffer. Metal ions such as Mn²⁺ and Ca²⁺ increased the proteolytic activity of the enzyme by 34 and 30 %, respectively, at 10 mM concentration. Cu²⁺ at 1 mM concentration was found to enhance the enzyme activity by 16 %, whereas inhibition was observed at higher concentration (>5 mM). Slight inhibition was observed even with lower (>1 mM) concentrations of Zn²⁺, Hg²⁺, Fe³⁺, Ni²⁺, and Co²⁺.The activity of protease was completely inhibited by phenylmethylsulfonyl fluoride, indicating that the VITP4 protease is a serine protease. The presence of ethylenediaminetetraacetic acid and 1,10-phenanthroline (>5 mM) moderately inhibited the activity, suggesting that the enzyme is activated by metal ions. The protease was purified to homogeneity with a purification fold of 15.7 with ammonium sulfate precipitation and 46.65 with gel filtration chromatography using Sephadex G-100, resulting in a specific activity of 424?±?2.6 U mg^?1. The VITP4 protease consists of a single polypeptide chain with a molecular mass of 34.7 kDa as determined by sodium dodecyl sulfate–polyacrylamide gel electrophoresis and matrix-assisted laser desorption/ionization–time of flight. Among the different substrates used (casein, egg albumin, gelatin, and bovine serum albumin), the activity was higher with casein with V _max, K _m, and k _cat values of 0.817 mg ml min^?1, 0.472 mg ml^?1, and 2.31 s^?1, respectively. Circular dichroism studies revealed that the VITP4 protease has a predominantly β-sheet structure (51.6 %) with a temperature for half denaturation of 85.8 °C in the presence of 1 mM CaCl₂. Additionally, the VITP4 protease was found to retain more than 70 % activity in the presence of 10 mM concentration of different detergents (CTAB, urea, and sodium dodecyl sulfate) and surfactants (Triton X-100, Tween-20, and Tween-80), and the results of wash performance test with various commercial detergents confirmed that it can be used in detergent formulations.     

Excellent electrocatalytic performance of a Ni<Superscript>2+</Superscript>-loaded multiwalled carbon nanotube composite in glucose oxidation

A new type of Ni²⁺-loaded MWCNT composite was prepared by mixing carboxylated multiwalled carbon nanotubes (MWCNTs) and Ni²⁺ ions and allowing them to interact electrostatically. The resulting composite was subsequently used as an electrocatalyst for glucose (Glu) oxidation. Compared with electrodes modified through the addition of free Ni²⁺ ions or MWCNTs, the Ni²⁺/MWCNT composite electrode showed greatly improved properties such as hydrophilicity. Investigations of the Ni²⁺/MWCNT composite electrode via inductively coupled plasma atomic emission spectroscopy and nitrogen adsorption–desorption isotherms verified that Ni²⁺ ions had been adsorbed onto the surfaces of the MWCNTs in the composite. As expected, a Ni²⁺/MWCNT composite-based sensor showed extraordinary electrocatalytic performance in Glu oxidation. In the concentration range 0–4.3 mM, a good linear relationship between the Glu added and the current generated was observed, with a correlation coefficient (R ²) of 0.9988. The detection limit and sensitivity were calculated to be 0.081 μM and 2285 μA mM^?1 cm^?2, respectively. Finally, the new method was successfully applied to determine the Glu in a human blood sample. Recoveries of >100%, indicative of high reliability, accuracy, and precision, were obtained.     

IR Spectroscopic Study of the Interaction of Transition Metal Ions with Hydroxyapatite Modified by Potassium Ferrocyanide

IR spectroscopy was used to study the modification of hydroxyapatite by potassium ferrocyanide and the interaction of transition metal ions with the modified adsorbent. The structural changes of hydroxyapatite upon the adsorption of Zn²⁺ ions were studied by X-ray phase analysis. Potassium ferrocyanide was found to interact with the surface hydroxyl groups of hydroxyapatite through the nitrogen unshared electron pair. Co²⁺, Ni²⁺, and Zn²⁺ ions were found to eliminate outer-sphere K⁺ ions of adsorbed ferrocyanide to give Fe²⁺— CN—M²⁺— NC—Fe²⁺ bridging structures. Zn²⁺ cations additionally eliminate a part of the Ca²⁺ ions from structural positions of hydroxyapatite, which leads to the appearance of a two-phase hydroxyapatite–sholzite system with heterogeneous distribution of the Ca²⁺ ions in the mot her mineral phase, while the Zr²⁺ ions are found in the new sholzite phase.     

Study of the gadolinium sorption on the C100 ion-exchange resin for the development of the antineutrino detector targets

Adsorption of the gadolinium from H₂O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd³⁺ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd³⁺ on C100 from H₂O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g^?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol^?1, ΔS = ? 90.27 J mol^?1 K^?1, ?H = ? 50.93 kJ mol^?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd³⁺ sorption on the C100 resin is reversible second order chemical reaction.     

Monitoring 60Co activity for the characterization of the sorption process of Co2+ ions in municipal activated sludge

In large volumes produced activated sludges from wastewater treatment plants (WWTPs) with low concentrations of heavy metals can be utilized as agricultural fertilizers and soil conditioners. Increased contents of toxic xenobiotics are limiting factors that affect the utilization of these heterogeneous wastes. The main aim of our paper was to show the utilization of dried activated sludge (DAS) from municipal WWTP as potential Co²⁺ ions sorbent i.e. for non-agricultural purposes. The radio indicator method by radionuclide ⁶⁰Co and γ-spectrometry for characterization DAS sorption properties was used. DAS soluble and solid fractions were characterized by biochemical, ETAAS and CEC analysis. The sorption of Co²⁺ ions by DAS was rapid process and equilibrium was reached within 2 h. Sorption capacity of DAS (Q) increased with the initial concentration of CoCl₂ in the range from 100 to 4,000 μmol l^?1, reaching 20 and 160 μmol g^?1. Obtained Q values were depent on pH value from 2.0 to 8.0. The maximum sorption capacity (Q _max) of DAS at pH 6 calculated from mathematical model of Langmuir adsorption isotherm was 175 ± 9 μmol g^?1. FT-IR analyses showed the crucial role of carboxyl functional groups of DAS surfaces on cobalt uptake. For confirmation ion-exchange mechanism in sorption process of Co²⁺ ions by DAS scanning electron microscopy and EDX analysis were used.     

A new Schiff base fluorescent indicator for the detection of Mg<Superscript>2+</Superscript> and its application to real samples

A new Schiff base fluorescence probe, 3-Allylsalicylaldehyde salicylhydrazone (L), for Mg²⁺ was designed and synthesized. The fluorescence of the sensor L was enhanced remarkably by Mg²⁺ with 2:1 binding ratio, and the binding constant was determined to be 1.02 × 10⁷ M^?1. Probe L had high sensitivity for Mg²⁺ in a solution of DMF/water (4:1, v/v, pH 7.5), and the detection limit was 4.88 × 10^?8 mol/L. Common coexistent metal ions, such as K⁺, Na⁺, Ag⁺, Ca²⁺, Zn²⁺, Ba²⁺, Bi²⁺, Cu²⁺, Ni²⁺, Hg²⁺, Fe³⁺ , and Al³⁺, showed little or no interference on the detection of Mg²⁺ in solution. The fluorescence probe L, which was successfully used for the determination of trace Mg(II) in real samples, was shown to be promising for liquid-phase extraction coupled with fluorescence spectra.