Solid phase extraction of ultra traces mercury (II) using octadecyl silica membrane disks modified by 1,3-bis(2-ethoxyphenyl)triazene (EPT) ligand and determination by cold vapor atomic absorption spectrometry

A facile and highly efficient method was developed for the preconcentration of the ultra trace amounts of mercury (II) ions. Octadecyl silica membrane disk was modified by the recently synthesized triazene ligand, 1,3-bis(2-ethoxyphenyl)triazene (EPT), and cold vapor atomic absorption spectrometry was used to determine the resultant preconcentrated Hg(II) ions. Solution studies with EPT and a series of metal ions were done in advance, and the results showed a strong affinity of EPT to the mercury ions. To perform solid phase extraction, various parameters such as pH of the sample, flow rates and the amount of the ligand were optimized. A linear calibration curve was obtained in the range of 0.02-1.90 μg L⁻¹ with r² = 0.9990 (n = 8), and the limit of detection (LOD) based on three times the standard deviation of the blank was 10.6 ng L⁻¹. The relative standard deviation (RSD) for the determination of 0.1 μg L⁻¹ Hg(II) found to be 2.9% while a RSD value of 1.1% was obtained for the determination of 1.0 μg L⁻¹ Hg(II) (n = 8). The preconcentration and improvement factors were 380 and 74, respectively. The newly developed method was successfully applied to the determination of mercury ions in real water samples.     

Synthesis and application of chloromethylated polystyrene modified with 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone (PPDOT) as a new sorbent for the on-line preconcentration and determination of copper in water, soil, and food samples by FAAS

In this paper, we report a simple and sensitive on-line solid phase extraction system for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry (FAAS). This method is based upon the on-line retention of copper at pH 5.0 on a minicolumn packed with chloromethylated polystyrene modified by 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone (PPDOT) as a new solid-phase extraction (SPE) sorbent. The retained Cu(II) ions were eluted with 1.0 M HNO₃, and transported directly to FAAS for determination. Several chemical and flow variables were studied and optimized for a quantitative preconcentration and determination of copper(II). At the optimized conditions, for preconcentration of 10.0 mL of a sample solution, a linear calibration graph was obtained over the concentration range of 3.00-120.0 μg L⁻¹ for Cu(II). The limit of detection (3σ), limit of quantification (10σ), and enrichment factor are 0.56 μg L⁻¹, 2.0 μg L⁻¹ and 41, respectively. The relative standard deviation (n = 6) at 20 μg L⁻¹ of Cu(II) is 2.0%. This method could be applied for determination of trace amounts of Cu(II) in water, soil, and food samples with satisfactory results.     

Biosorption of cadmium (II) and lead (II) from aqueous solutions using mushrooms: A comparative study

Sorption capacity of oyster mushroom (Pleurotus platypus), button mushroom (Agaricus bisporus) and milky mushroom (Calocybe indica) were evaluated on biosorption of heavy metals, viz. cadmium (II) and lead (II) from aqueous solutions. The optimum sorption conditions were studied for each metal separately. The desired pH of the aqueous solution was found to be 6.0 for the removal of cadmium (II) and 5.0 for removal of lead (II) for all the mushrooms. The percent removal of both the metals was found to increase with the increase in biosorbent dosage and contact time. The fitness of the biosorption data for Langmuir and Freundlich adsorption models was investigated. It was found that biosorption of cadmium (II) and lead (II) ions onto the biomass of the three mushrooms were better suitable to Langmuir than Freundlich adsorption model. P. platypus showed the highest metal uptake potential for cadmium (q_max 34.96 mg/g) whereas A. bisporus exhibited maximum potential for lead (q_max 33.78 mg/g). Milky mushroom showed the lowest metal uptake capacity for both the metals. The present data confirms that mushrooms may be used as efficient biosorbent for the removal of cadmium (II) and lead (II) ions from aqueous solution.     

Solid-state synthesis of amorphous iron(III) phosphate at room temperature and its absorption properties for Hg(II) and Ag(I) ions

Amorphous iron(III) phosphate has been synthesized by solid-state reaction at room temperature and was characterized by several methods. The non-crystalline sample displayed the particle size within the range of 100-200 nm, and it had a strong fluorescence emission peak centered at 306.6 nm. Moreover, its absorption properties for Hg(II) and Ag(I) heavy metal ions have been investigated. The experimental research results revealed that its excellent absorption capacity for Hg(II) and Ag(I) could reach to 1.831 mmol/g and 1.354 mmol/g, respectively, at pH = 5.98 and the absorption time t = 6 h. The absorption properties for Hg(II) were usually stronger that those for Ag(I).     

Silica-[Fe(bpy)3] composite particles with photo-responsive change of color and magnetic property

Photo-induced complex formation of tris-2,2′-bipyridine iron(II) complex ([Fe(bpy)₃]²⁺) from the mixture of FeCl₃ and 2,2′-bipyridine was achieved in silica gel containing 150-300 μm silica particles, derived from a complex emulsion with HCl aqueous solution and tetraethyl orthosilicate (TEOS). More than 95% of Fe(III) and 2,2′-bipyridine were incorporated in silica particles. Yellow-red color change, due to [Fe(bpy)₃]²⁺, was observed by irradiation with 365 nm UV beam at 0.3 mW cm⁻² for 120 s. The complex formation accompanies simultaneous spin transition from the high-spin state of Fe(III) to the low-spin state of Fe(II).     

Isotherms and thermodynamics for the sorption of heavy metal ions onto functionalized sporopollenin

In this study, sporopollenin of Lycopodium clavatum spores was used for the sorption experiment. Glutaraldehyde (GA) immobilized sporopollenin (Sp), is employed as a sorbent in sorption of selected heavy metal ions. The sorbent prepared by sequential treatment of sporopollenin by silanazing compound and glutaraldehyde is suggested for sorption of Cu(II), Zn(II) and Co(II) from aqueous solutions. Experimental conditions for effective sorption of heavy metal ions were optimized with respect to different experimental parameters using batch method in detail. Optimum pH range of Cu(II) has occurred at pH ≥ 5.5 and Zn(II), Co(II) at pH ≥ 5.0, for the batch method. All of the metal ions can be desorbed with 10 cm³ of 0.5 mol dm⁻³ of ethylenediaminetetraacetic acid (EDTA) solution. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm equations were applied to the experimental data. Thermodynamic parameters such as free energy (ΔG^o), entropy (ΔS^o) and enthalpy (ΔH^o) were also calculated from the sorption results used to explain the mechanism of the sorption. The results indicated that this sorbent is successfully employed in the separation of trace Cu(II), Zn(II) and Co(II) from the aqueous solutions.     

Dependency of eutectic spacings and microhardness on the temperature gradient for directionally solidified Sn–Ag–Cu lead-free solder

Sn–3.5 wt.%Ag–0.9 wt.%Cu alloy was directionally solidified upward at a constant growth rate (V = 7.20 μm s⁻¹) with different temperature gradients (G = 2.48–6.34 K mm⁻¹) by using a Bridgman type directional solidification furnace. The eutectic microstructures of directionally solidified Sn–3.5 wt.%Ag–0.9 wt.%Cu alloy were observed to be plate and rod structures from quenched samples. The values of eutectic spacings (λ) and microhardness (H_V) were measured from both transverse and longitudinal sections of the samples. The dependence of eutectic spacings (λ) and microhardness (H_V) on the temperature gradient (G) were determined by using linear regression analysis. According to these results, it has been found that, the value of λ decreases with the increasing the value of G and whereas, the value of H_V increases for a constant growth rate. The results obtained in the present work were also compared with the previous similar experimental results obtained for binary and ternary alloys.     

XAS characterization of the RuO2–Ta2O5 system local (crystal) structure

The influence of the preparation method on the structural properties of the RuO₂–Ta₂O₅ system was investigated. Both thin films on Ti substrates and powder samples of nominal composition Ti/RuO₂–Ta₂O₅ (Ru:Ta = 100:0, 90:10, 80:20, 30:70, and 0:100 at.%) were prepared through thermal decomposition of polymeric precursors (DPP). The thin films and powder samples were investigated using X-ray absorption spectroscopy (XAS). XANES analyses showed that Ru and Ta are present in the Ru(IV) and Ta(V) oxidation states. EXAFS signals of all the samples were analyzed, to obtain the average bond length (r), coordination number, and the Debye–Waller factor (σ²) for each Ru–O, Ru–Ru, Ta–O nearest-neighbor. The first shell Ru–O distance was found at 1.91–1.92 Å with coordination number of 1.8–2.1, and at 2.01–2.02 Å with coordination number of 3.9–4.1. The Ta–O distance obtained for all the samples and in both modes (transmission and fluorescence) had significantly different values from the theoretical ones. The results revealed that the local structure around both the Ru and Ta sites are similar, and that they consist of distorted M–O₆ octahedra (where M = Ru or Ta).     

Poly(acrylamide) functionalized chitosan: An efficient adsorbent for azo dyes from aqueous solutions

In the present communication we report on the optimization of persulfate/ascorbic acid initiated synthesis of chitosan-graft-poly(acrylamide) (Ch-g-PAM) and its application in the removal of azo dyes. The optimum yield of the copolymer was obtained using 16 × 10⁻² M acrylamide, 3.0 × 10⁻² M ascorbic acid, 2.4 × 10⁻³ M K₂S₂O₈ and 0.1 g chitosan in 25 mL of 5% aqueous formic acid at 45 ± 0.2 °C. Ch-g-PAM remained water insoluble even under highly acidic conditions and could efficiently remove Remazol violet and Procion yellow dyes from the aqueous solutions over a pH range of 3–8 in contrast to chitosan (Ch) which showed pH dependent adsorption. The adsorption data of the Ch-g-PAM and Ch for both the dyes were modeled by Langmuir and Freundlich isotherms where the data fitted better to Langmuir isotherms. To understand the adsorption behavior of Ch-g-PAM, adsorption of Remazol violet on to the copolymer was optimized and the kinetic and thermodynamic studies were carried out taking Ch as reference. Both Ch-g-PAM and Ch followed pseudo-second-order adsorption kinetics. The thermodynamic study revealed a positive heat of adsorption (ΔH°), a positive ΔS° and a negative ΔG°, indicating spontaneous and endothermic nature of the adsorption of RV dye on to the Ch-g-PAM. The Ch-g-PAM was found to be very efficient in removing color from real industrial wastewater as well, though the interfering ions present in the wastewater slightly hindered its adsorption capacity. The data from regeneration efficiencies for ten cycles evidenced the high reusability of the copolymer in the treatment of waste water laden with even high concentrations of dye.     

Electrical resistivity of the hole doped La0.8Sr0.2MnO3 manganites: Role of electron–electron/phonon/magnon interactions

In this work, a quantitative analysis of reported metallic and insulating behaviour of resistivity in perovskite manganites La_0.8Sr_0.2MnO₃ is established. An effective inter-ionic interaction potential (EIoIP) with the long-range Coulomb, van der Waals (vdW) interaction and short-range repulsive interaction up to second-neighbour ions within the Hafemeister and Flygare approach was employed to estimate the Debye and Einstein temperature and was found to be consistent with the available experimental data. The electrical resistivity data in low temperature regime (T < T_MI) were theoretically analyzed within the framework of the classical electron–phonon model of resistivity, for example, the Bloch–Gruneisen (BG) model. The Bloch–Gruneisen (BG) model and terms T², T^4.5 simplify the electron–phonon, electron–electron and electron–magnon scattering processes. On the other hand, in high temperature regime (T > T_MI) the insulating nature is discussed with Mott's variable range hopping (VRH) model and small polaron conduction (SPC) model. For T > T_MI SPC model is more appropriate than the VRH model. The SPC model consistently retraces the higher temperature resistivity behaviour (T > θ_D/2). The metallic and semiconducting resistivity behaviours of La_0.8Sr_0.2MnO₃ manganites are analyzed, to the knowledge, for the first time highlighting the importance of electron–phonon, electron–electron, electron–magnon interactions and small polaron conduction.     

Use of rice straw as biosorbent for removal of Cu(II), Zn(II), Cd(II) and Hg(II) ions in industrial effluents

Adsorption experiments were carried out using waste rice straw of several kinds as a biosorbent to adsorb Cu(II), Zn(II), Cd(II) and Hg(II) ions from aqueous solutions at room temperature. To achieve the best adsorption conditions the influence of pH and contact time were investigated. The isotherms of adsorption were fitted to the Freundlich equation. Based on the experimental data and Freundlich model, the adsorption order was Cd(II) > Cu(II) > Zn(II) > Hg(II) on the rice straw. This quick adsorption process reached the equilibrium before 1.5 h, with maximum adsorptions at pH 5.0. Thermodynamic aspects of the adsorption process were investigated. The biosorbent material was used in columns for the removal of ions Cu, Zn, Cd and Hg of real samples of industrial effluent and its efficiency was studied.     

Synthesis, characterization and magnetic properties of hexagonal (VO)0.09V0.18Mo0.82O3 · 0.54H2O microrods

(VO)_0.09V_0.18Mo_0.82O₃ · 0.54H₂O microrods have been synthesized for the first time via a hydrothermal treatment of aqueous peroxomolybdic acid and vanadyl sulfate. The compound crystallizes in hexagonal rods with space group P6₃, and lattice constants a = 10.586 Å, and c = 3.698 Å. The single crystalline rods exhibit diameters of 1-2 μm and lengths up to 45 μm. A variety of techniques, including X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscope, Fourier-transform infrared spectroscopy, differential scanning calorimetry and static magnetometry were used to characterize the product.     

Microstructure and martensitic transformation in Si-coated TiNi powders prepared by ball milling

Si was coated on the surface of Ti–49Ni (at%) alloy powders by ball milling in order to improve the electrochemical properties of the Si electrodes of secondary Li ion batteries and then the microstructure and martensitic transformation behavior were investigated by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Ti–Ni powders coated with Si were fabricated successfully by ball milling. As-milled powders consisted of highly deformed Ti–Ni powders with the B2 phase and amorphous Si layers. The thickness of the Si layer coated on the surface of the Ti–Ni powders increased from 3–5 μm to 10–15 μm by extending the milling time from 3 h to 48 h. However, severe contamination from the grinding media, ZrO₂ occurred when the ball milling time was as long as 48 h. By heating as-milled powders to various temperatures in the range of 673–873 K, the highly deformed Ti–Ni powders were recovered and Ti₄Ni₄Si₇ was formed. Two-stage B2–R–B19′ transformation occurred when as-milled Si-coated Ti–49Ni alloy powders were heated to temperatures below 873 K, above this temperature one-stage B2–B19′ transformation occurred.     

Development of a specific and highly sensitive optical chemical sensor for determination of Hg(II) based on a new synthesized ionophore

A novel optode for determination of Hg(II) ions is developed based on immobilization of a recently synthesized ionophore, 7-(1H-imidazol-1-ylmethyl)-5,6,7,8,9,10-hexahydro-2H-1,13,4,7,10 benzodioxatriaza cyclopentadecine-3,11(4H,12H)-dione, in a PVC membrane. Dioctyl sebacate was used as a plasticizer, sodium tetraphenylborate as an anionic additive and ETH5294 as a chromoionophore. The response of the optode was based on the complexation of Hg(II) with the ionophore in the membrane phase, resulting an ion exchange process between Hg(II) in the sample solution and H⁺ in the membrane. The effects of pH and amounts of the ionophore, chromoionophore, ionic additive and type of plasticizer on the optode response were investigated. The selectivity of the optode was studied in the present of several cations. The optode has a linear response to Hg(II) in the range of 7.2 × 10^? 13–4.7 × 10^? 4 mol L^? 1 with detection limit of 0.18 pmol L^? 1. The optode was successfully applied to the determination of Hg(II) in real samples.     

Fabrication of (K, Na)NbO3 glass-ceramics and crystal line patterning on glass surface

Crystallization behavior of (30−x)K₂O-xNa₂O-25Nb₂O₅-45SiO₂ (KNNS; x = 0, 5, 10, 20 and 30) (mol%) glasses was clarified and perovskite-type nonlinear optical (K, Na)NbO₃ (KNN) crystals were synthesized by using a conventional glass-ceramics method. It was found that Na₂O amounts over around x = 10 mol% were necessary to form perovskite-type KNN crystals showing second-harmonic generations. The substitution of K⁺ and Na⁺ ions was confirmed from X-ray diffraction (XRD) analysis. A continues-wave of Yb:YVO₄ fiber laser (wavelength: 1080 nm) was irradiated onto CuO doped KNNS; x = 10 (Cu-KNNS) surface. The absorption coefficient of this Cu-KNNS glass was determined to be α = 5.0 cm⁻¹. Perovskite-type KNN crystals were patterned in the condition of the laser power of >1.20 W and the laser scanning speed of S = 7 μm/s, and their structure was determined by Raman scattering spectra and XRD analysis.     

Study on field emission and photoluminescence properties of ZnO/graphene hybrids grown on Si substrates

Zinc oxide/graphene (ZnO/G) hybrids are prepared on n-Si (1 0 0) substrates by electrophoretic deposition and magnetron sputtering technique. The crystal structure, morphology and photoluminescence (PL) properties of the ZnO/G hybrids are analyzed via X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and fluorescence–phosphorescence spectrometer, respectively. The results indicate that the crystal quality of ZnO nanostructure deteriorates after depositing graphene buffer layer. Whereas many three dimensional stacking blowballs form in the ZnO/G hybrid, creating a larger surface area than that of ZnO nanostructure. The photoluminescence (PL) spectrum of the ZnO/G hybrid contains multi-peaks, which are consistent with ZnO nanostructure except for two new peaks at 390 and 618 nm. In addition, field emission measurement reveals that E_to and E_thr decrease from 8.01 V μm⁻¹ and 14.90 V μm⁻¹ of the ZnO nanostructure to 2.72 V μm⁻¹ and 7.70 V μm⁻¹ of the ZnO/G hybrid. ZnO/G hybrid is characteristic of having excellent emitting behavior suitable for application in field emission technology.     

Aqueous two-phase systems: a new approach for the determination of p-aminophenol

A new method has been developed for the spectrophotometric determination of p-aminophenol (PAP) in water, paracetamol formulations and human urine samples with a recovery rate between 94.9 and 101%. This method exploits an aqueous two-phase system (ATPS) liquid-liquid extraction technique with the reaction of PAP, sodium nitroprusside and hydroxylamine hydrochloride in pH 12.0, which produces the [Fe₂(CN)₁₀]¹⁰⁻ anion complex that spontaneously concentrates in the top phase of the ATPS (K[Fe₂(CN)₁₀]¹⁰⁻=97.7). The ATPS does not require an organic solvent, which is a safer and cleaner liquid-liquid extraction technique for the determination of PAP. The linear range of detection was from 5.00 to 500 μg kg⁻¹ (R ≥ 0.9990; n = 8) with a coefficient of variation of 2.11% (n = 5). The method exhibited a detection limit of 2.40 μg kg⁻¹ and a quantification limit of 8.00 μg kg⁻¹. The ATPS method showed a recovery that ranged between 96.4 and 103% for the determination of PAP in natural water and wastewater samples, which was in excellent agreement with the results of the standard 4-aminoantipyrine method that was performed on the same samples.     

Ion beam induced interface mixing of Ni on PTFE bilayer system studied by quadrupole mass analysis and electron spectroscopy for chemical analysis

We have investigated interfacial chemistry in a 100 nm Ni on PTFE (polytetrafluoroethylene) bilayer system induced by 120 MeV Au ions with fluences varying from 1 × 10¹² to 5 × 10¹³ ions/cm². In-situ quadrupole mass analysis (QMA) shows emission of Fluorine (F) and different fluorocarbons (C_xF_y) such as CF, CF₃, C₂F₃ etc. during irradiation. Electron spectroscopy for chemical analysis (ESCA) studies show that Ni reacts with chemically reactive species such as F⁻/F and C_xF_y ions or radicals emitted during irradiation forming NiF₂ and metal-polymer complexes (-CFNi-). Rutherford backscattering spectrometry (RBS) was used to analyze the atomic transport at the interface and strong interface mixing is observed at the ion fluence 5 × 10¹³ ions/cm². Atomic force microscopy (AFM) studies before and after irradiation show that surface roughness is increased from 6.9 to 12.4 nm with increasing fluence. Observed results have been explained on the basis of the chemical reactions taking place within molten ion tracks in the polymer and hot zones around the ion paths created in the Ni film. The studies show that swift heavy ion irradiation introduces strong chemical alteration in the system and induces chemical reactions within the ion track, which enhance ion beam mixing in Ni-PTFE bilayer systems.     

Development of a Spectrophotometric Optode for the Determination of Hg(II)

A new simple and inexpensive optical chemical sensor for mercury(II) ions is presented. The mercury sensing system has prepared by incorporating of l-[2-pyridylazo]-2-naphthol as a suitable ligand for Hg(II) on triacetyl cellulose. The proportionality in intensity of the membrane color on the optodes loaded with varying amounts of Hg(II) suggests its potential applications for screening of Hg(II) in aqueous samples by visual colorimetry. The optode has a dynamic range 1.0 to 1000.0 muM with a limit of detection of 0.8 muM Hg(II). Different experimental parameters such as variable affecting on sensor preparation and pH of the sample solution plus response time were studied. The optodes developed in the present work were found to be stable, cost effective, easy to prepare, and efficient for direct determination of Hg(II) in a variety of aqueous samples using spectrophotometric method.     

Visible-light photocatalytic activity of semiconductor composites supported by electrospun fiber

The preparation and photocatalysis of TiO₂–ZnS/fluoropolymer fiber composites were investigated. The fluoropolymer nanofiber mats with carboxyl groups were prepared by electrospinning, and then titanium and zinc ions were introduced onto the fiber surfaces by the coordinating of carboxyl of fluoropolymer in solution. The TiO₂–ZnS composites with diameters 15 nm to 1 μm were immobilized on the surface of fluoropolymer electrospun fiber using hydrothermal synthesis. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis reveal that some chemical interaction exists between TiO₂–ZnS composites and fluoropolymer fibers, so the semiconductor composites were immobilized tightly on the surface of fluoropolymer fibers. The ultraviolet–visible absorption spectra show the TiO₂–ZnS/fluoropolymer fiber composites have low band gap and good visible-light response ability. The degradation rate of methylene blue in TiO₂–ZnS/fluoropolymer fiber composites system was considerably higher than that of TiO₂ or TiO₂–ZnS nanoparticles system under visible-light irradiation, because the TiO₂–ZnS/fluoropolymer fiber composites possess good visible-light response ability, high specific surface areas, and adsorption–migration–photodegradation process. The photocatalytic activity of TiO₂–ZnS/fluoropolymer fiber composites changes indistinctively after 10 repeating photocatalysis tests.