Oxidized multiwalled carbon nanotubes modified with 2-(2-hydroxy-5-nitrophenyl)-4,5-diphenyl imidazole for solid phase extraction and preconcentration of some metal ions

In this work, a new procedure for the enrichment of the trace amount of Cu²⁺, Ni²⁺, Co²⁺, Pb²⁺, Fe²⁺, and Zn²⁺ ions based on the utilization of multiwalled carbon nanotubes (MWCNT) modified with 2-(2-hydroxy-5-nitrophenyl)-4,5-diphenyl imidazole as chelating agent prior to their determination by flame atomic absorption spectrometry has been described. The influence of effective parameters including pH, amount of ligand and MWCNT, composition of eluent, and coexisting ions on recoveries of understudy metal ions was examined. At the optimum pH of 5.0, all metal ions were quantitatively sorbed onto the proposed solid phase and completely desorbed with 8?mL of 5.0?mol?L^?1 HNO₃. The detection limit of Cu²⁺, Co²⁺, Ni²⁺, Pb²⁺, Fe²⁺, and Zn²⁺ ions was 1.7, 2.4, 2.3, 2.9, 2.8, and 1.4?µg?L^?1, while the preconcentration factor was 63 for Cu²⁺ and 94 for the other metal ions and relative standard deviations between 1.8 less than 3.0%. The proposed procedure was applied for the analysis of various samples.     

Online solid phase preconcentration using EGDMA–MAA copolymer for lead determination by FAAS

A Ethylene glycol dimethacrylate (EGDMA) methacrylic acid (MAA) resin was used for preconcentration of lead at trace levels in water samples. For this purpose, a flow-injection, solid phase extraction method was developed for the determination of lead by flame atomic absorption spectrometry. Lead ions were sorbed on a EGDMA–MAA column at pH 4, followed by an elution step using 288 µL of 4.0 M nitric acid solution and determination by flame atomic absorption spectrometry. Optimum conditions for quantitative sorption involving the pH, sample volume, loading and elution flow rates, eluent type, and volume were investigated. A 868-fold enrichment factor could be reached. The detection limit for the water samples, estimated from the noise on the signal obtained for 250 mL of 10 µg L^?1 loaded at 4.9 mL min^?1 was 1.04 µg L^?1. The method was applied for lead determination in river water samples collected in Edirne, Turkey. Recoveries of spiked solutions (10 µg L^?1) to river water samples were quantitative. Finally, the method was validated by the analysis of certified reference material SRM 2704 (Buffalo River Sediment).     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

Determination of Au(III) and Pd(II) ions by flame atomic absorption spectrometry in some environmental samples after solid phase extraction

A simple and sensitive solid phase extraction method was developed for simultaneous separation and preconcentration of gold and palladium ions with N-(4-methylphenyl)-2-{[(4-phenyl-5-pyridine-4-yl-4H-1,2,4-triazol-3-yl)thio]acetyl}hydrazine carbo thioamide complex on Amberlite XAD-1180 resin before their determination by flame atomic absorption spectrometry. Some analytical parameters such as HNO₃ concentration of the sample solution, amount of complexing agent, sample volume, eluent type and volume, effects of foreign ions and adsorption capacity of the resin were investigated for quantitative recovery of gold and palladium ions. The effects of some anions and cations were also examined. Under optimum conditions, the detection limits for gold and palladium ions were found to be 0.29 and 0.19 μg L^?1, respectively. The preconcentration factor for gold and palladium was 250. After being validated by standard addition and analysis of standard reference material, the procedure was successfully applied to the analysis of sea and stream water, anodic slime, gold ore, soil and electronic waste.     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Hepatoprotective activity of 1-(4-(Dimethylamino)Benzylidene)-5-(2-Oxoindolin-3-ylidene) Thiocarbohydrazone in rats

The aim of the present study was to evaluate the hepatoprotective activity of 1-(4-(dimethylamino)benzylidene)-5-(2-oxoindolin-3-ylidene) thiocarbohydrazone, a novel isatin derivative against carbon tetrachloride (CCl₄)-induced hepatotoxicity in rats. Hepatic damage was induced by administration of CCl₄ (1 ml/kg, b.w., p.o.) in combination with liquid paraffin (1:1) as a single dose. The hepatotoxic rats were treated with test compound at doses of 50 or 100 mg/kg for three days and liver damage biomarkers, including activities of serum glutamate pyruvate transaminase (SGPT), serum glutamate oxaloacetate transaminase (SGOT), serum alkaline phosphatase (ALP), and levels of total serum bilirubin (TB) measured in blood samples. Results demonstrated that treatment with test compound at doses of 50 or 100 mg/kg to hepatotoxic rats produced a significant dose-dependent reduction of elevated SGOT, SGPT, ALP activities and TB levels indicating a hepatoprotective effect that was confirmed by histopathological examination of liver tissues. The study results confirmed the hepatoprotective activity of 1-(4-(dimethylamino)benzylidene)-5-(2-oxoindolin-3-ylidene) thiocarbohydrazone in rats.     

In vitro antioxidant and antibacterial activities of certain 3-{4-(5-mercapto-1,3,4-oxadiazole-2-yl)phenylimino}-indolin-2-one derivatives

A new series of 5- or 7-substituted 3-{4-(5-mercapto-1,3,4-oxadiazol-2-yl)phenylimino}-indolin-2-one derivatives were screened for in vitro antioxidant and antimicrobial activities. The results of this study revealed that all synthesized compounds were significantly scavenged DPPH free radicals in a concentration-dependant manner. The IC₅₀ values of all test compounds were found to be between 18.34 and 50.54?µM. All compounds significantly inhibited growth of bacteria and most of the minimum inhibitory concentration values were between 20 and 100?mg?mL^?1 indicating potent to moderate antibacterial activity. In conclusion, 3-{4-(5-mercapto-1,3,4-oxadiazole-2-yl)phenylimino)-5 or 7-substituted indolin-2-ones derivatives exhibited moderate antioxidant and antimicrobial activities.     

Application of Zr(IV) tungstate for removal of metal ions from aqueous solutions

A heteropolyacid Zr(IV) tungstate-based cation exchanger has been synthesized. An amorphous sample, prepared at pH 1.2 and having a Na⁺ ion exchange capacity of 0.92?meq?g^?1, was selected for further studies. Its physicochemical properties were determined using Fourier transform infrared spectrometer, X-ray diffraction, thermogravimetric, and scanning electron studies. To understand the cation exchange behavior of the material, distribution coefficients (K _d) for metal ions in various solvent systems were determined. Some important binary separations of metal ions, namely Mg²⁺–Bi³⁺, Cd²⁺–Bi³⁺, Fe³⁺–Bi³⁺, Th⁴⁺–Bi³⁺, and Fe³⁺–Zn²⁺, were achieved on such columns. The practical utility of these separations was demonstrated by separating Fe³⁺ and Zn²⁺ ions quantitatively in commercial pharmaceutical formulation. The cation exchanger has been successfully applied also for the treatment of industrial wastewater and a synthetic mixture. All the results suggests that Zr(IV) tungstate has excellent potential for the removal of metals from aqueous systems using packed columns of this material.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.     

Selective separation and preconcentration studies of chromium(VI) with Alamine 336 supported liquid membrane

Chromium compounds have received considerable attention because these are used extensively in such industrial applications as electroplating, steelmaking, tanning of leather goods, and corrosion inhibition. The use of supported liquid membranes (SLMs) to remove metals from wastewaters has actively been pursued by the scientific and industrial community. In the present work, the selective separation and preconcentration of Cr(VI) ions has been studied by using a commercial amine as the membrane liquid on the porous polypropylene support. Permeation experiments were conducted on a laboratory scale batch reactor made up of perspex, with a memberane fixed amid the two chambers. The flux of Cr(VI) ions was found to be maximum (3.15?×?10^?5?mol?cm^?2?s^?1) around pH 1. Above and below this pH the flux decreases. Distribution studies show that an increase in the amine concentration leads to higher distribution coefficients at fixed pH values. At pH around unity, the distribution of Cr(VI) ions into the organic phase was found to be maximum, of the order of 56.3. The Cr(VI) transport through the membrane increases with rise in temperature. In order to check the long-term efficiency of the flat sheet SLM, an experiment was conducted with higher Cr(VI) concentration (5000?ppm) for 24?h, at optimised parameters. It was observed that in 24?h, about 1/5th of the feed Cr(VI) is left over while the rest is transported. However, minute organic droplets were also seen in the feed and strip compartments, after 1 day. This observation suggested the loss of membrane liquid. The feasibility of preconcentration of Cr(VI) by using the proposed SLM parameters, was also studied by using the hollow fibre (HF) system. Highest enrichment factor (E.F) value was obtained for 50?mg?L^?1 whereby all of the metal was transported to the stripping phase and the resulting Cr concentration was 688?mg?L^?1 (E.F?=?13.8). It was observed that while treating more diluted solutions, the enrichment factor decreases. The values of E.F equal to 8.9 and 11.3 were found for initial Cr concentration of 10 and 30?mg?L^?1.     

Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L^?1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.     

A simple ligandless microextraction method based on ionic liquid for the determination of trace cadmium in water and biological samples

A simple and efficient ionic liquid-based ligandless microextraction method has been developed for preconcentration of cadmium ions (Cd²⁺) as a step prior to its determination by flame atomic absorption spectrometry (FAAS) with a micro-sample introduction system. In this approach, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] and ethanol were used as extractant and dispersive solvents to preconcentrate the Cd²⁺ in different waters, acid digested scalp hair, and nail samples. Some analytical parameters influencing the extraction efficiency of Cd²⁺ and its subsequent determination, including pH, IL volume, dispersant solvent volume, sample volume, temperature, incubation time, and matrix effect, were optimized. Under optimal conditions, the limit of detection (LOD), limit of quantification (LOQ), and enhancement factor (EF) were 0.4 μg L^?1, 1.3 μg L^?1, and 50, respectively. The relative standard deviation (RSD) of 100 μgL^?1 Cd²⁺ was 4.3% (n = 6). The validity of the proposed method was checked by determining Cd²⁺ in certified reference material (TM-25.3 fortified water) and standard addition; the results showed sufficient recovery (>98%) of Cd²⁺ within the certified value. The method was applied for preconcentration and determination of cadmium in waters and biological samples.     

新型阻燃剂TCPP对斑马鱼的毒性研究

为了明确新型阻燃剂磷酸三(2-氯丙基)酯(TCPP)的生态风险,本研究采用斑马鱼为模式生物,评价了TCPP对成鱼和胚胎的毒性效应。急性毒性研究结果表明,TCPP对斑马鱼成鱼的96 h致死中浓度(LC50)为47.06 mg·L~(-1),而对胚胎96 h-LC50为26.01 mg·L~(-1),且会影响胚胎的正常发育,导致孵化出的仔鱼产生畸形。成鱼14 d延长毒性试验结果表明,TCPP对斑马鱼成鱼的无可观察效应浓度(NOEC)为1.00 mg·L~(-1),染毒暴露后肝脏和性腺指数随TCPP浓度增加轻微下降,但肝脏中卵黄蛋白原(VTG)的含量和性腺中芳香化酶的活性随TCPP浓度增加普遍升高。此外,TCPP的暴露还会导致斑马鱼脑垂体中合成促性腺激素的相关基因表达量增加。因此,TCPP对斑马鱼成鱼和胚胎的急性毒性均为低毒级,但长期暴露会干扰内分泌系统的调控功能,影响斑马鱼的正常发育。     

TAR柱前络合、毛细管电泳分析痕量金属离子

1　IntroductionTransitionmetalswereamongthemostconcernelementsinenvironmentalanalysisduetotheirpotentialrolestoplantandanimals[1 ].Theserolesoftransitionmetalsinenvironmentdependedontheirconcentrationinthesoil,waterandlivingthings.Currently ,themostutiliz…     

Suitability of various chemically prepared activated carbons for the removal of copper(II) ions

Studies on the suitability of various chemically prepared activated carbons (CPACs) like straw carbon (SC), sawdust carbon (SDC), dates nut carbon (DNC) and commercial activated carbon (CAC) for the removal of copper(II) ions by adsorption from simulated wastewater have been carried out under batch mode at 30?±?1°C and the results are compared. The percentage removal of Cu(II) ions increased with a decrease in initial concentration, particle size and added electrolytes (ionic strength) and increased with an increase in contact time, dose of adsorbent and initial pH of the solution. The adsorption data were fitted with the Langmuir isotherm. The applicability of the first order kinetic equation viz. Lagergren equation was tested by correlation analysis. The adsorption process is concluded to be a spontaneous, first order reaction, occurring with increased randomness at the solid–liquid interface. Studies on the desorption of Cu²⁺-loaded activated carbons (ACs) were carried out with nitric acid (0.2–1?N). The possibility of reuse of the regenerated ACs in cycle (in cue-one after another) was tested. SC was found to be a suitable adsorbent alternative to CAC among CPACs for the removal of metal ions, in general, and Cu²⁺ ions, in particular.     

Determination trace amounts of copper, nickel, cobalt and manganese ions in water samples after simultaneous separation and preconcentration

In the present article, a simple, rapid, sensitive and economical method has been developed for the simultaneous separation and preconcentration of the trace amounts of copper, nickel, cobalt and manganese in water samples by using modified XAD-4 resins. The sorption was quantitative in the pH range 6.0–9.0, whereas quantitative desorption occurred instantaneously with 5.0 mL of 2 M HNO₃, and selected elements have been determined by using flame atomic absorption spectrometry. Dynamic ranges were 0.04–3.5, 0.1–6.0, 0.04–4.5 and 0.04–4.0 μg/mL for copper, nickel, cobalt and manganese, respectively. The detection limits were 9.2, 28.6, 12.3 and 5.7 ng/mL for Cu(II), Ni(II), Co(II) and Mn(II), respectively. The effects of the experimental parameters, including the sample pH, eluent type, interference ions and breakthrough volume, were studied for separation and preconcentration of Cu(II), Ni(II), Co(II) and Mn(II) ions. Determination of these ions in standard samples confirmed that the proposed method has good accuracy. The proposed method was used for the determination of these ions in water samples.     

Solid phase extraction of Cu (II), Ni (II), Co (II), and Fe (III) ions in water samples using salicylaldehyde benzoylhydrazone on Amberlite XAD-4 and their determinations by flame atomic absorption spectrometry

A multi element preconcentration procedure for solid phase extraction on Amberlite XAD-4 as their salicylaldehyde benzoylhydrazone chelates and flame atomic absorption spectrometric determination of some trace metal ions in water samples are proposed in this work. The influences of some analytical parameters, including pH of aqueous solution, amounts of reagent, flow rates of sample and eluent solutions, and sample volume on the quantitative recoveries of copper, nickel, cobalt, and iron were investigated. The effects of concomitant ions on the retentions of the analytes were also examined. The developed method has been successfully applied to the determination of metal ions in some real samples, including, tap water, river water, spring water, and waste water.     

Photocatalytic degradation of chlorophenols using Ru(bpy) 3 2+ /S2O 8 2−

Advanced oxidation processes, such as photocatalysed oxidation, provide an important route for degradation of wastes. In this study, the lowest excited state (³MLCT) of Ru(bpy)₃²⁺ is used to break down chlorophenol pollutant molecules to harmless products. This has the advantage of using visible light and a short-lived catalytically active species. Photolysis of deaerated aqueous solutions of a variety of mono- and poly-substituted chlorophenols has been followed in the presence of Ru(bpy)₃²⁺/S₂O₈²⁻ with near visible light (λ > 350 nm) by UV/visible absorption spectroscopy, luminescence, potentiometry, NMR and HPLC techniques. Upon irradiation, a decrease is observed in the chlorophenol concentration, accompanied by the formation of Cl⁻, H⁺ and SO₄²⁻ ions as the main inorganic products. Benzoquinone, phenol, dihydroxybenzenes and chlorinated compounds were the dominant organic products. As the ruthenium(II) complex is regenerated in the reaction, the scheme corresponds to an overall catalytic process. The kinetics of the rapid chlorophenol photodechlorination has been studied, and are described quite well by pseudo-first order behaviour. Further studies on this were made by following Cl⁻ release with respect to the initial Ru(bpy)₃²⁺ and S₂O₈²⁻ concentrations. A comparison is presented of the photodechlorination reactivity of the mono and polychlorophenols studied at acidic and alkaline pH.     

Toxic effects of dietary of Al3+ ions in tilapias (Oreochromis niloticus) and protective effect of Zn2+ ion

The lethal effects of aluminum ion (Al³⁺) in tilapia (Oreochromis niloticus) raised in concrete tanks were investigated. Tilapias were fed daily with commercial feed enriched with known concentrations of Al³⁺ and analyzed by differential pulse anodic stripping voltammetry (DPASV). The concentrations of Al³⁺ in feces, water, muscle tissue, viscera, and heads were determined every 3 months for a period of 365 days. The Tilapia head was the most affected tissue by Al³⁺. In general, Al³⁺ bioaccumulation reached the lethal dose (LD₅₀) after 335 days of experiment as follows: 34.9?mg?kg^?1 (muscle tissue), 88.2?mg?kg^?1 (viscera), and 126.9?mg?kg^?1 (head without gills). After determining Cu²⁺, Zn²⁺, and Ca²⁺ by absorption spectrometry, a decrease in the Ca²⁺ concentration was noted in the head during the experimental period. These observations were associated with the occurrence of a decalcification in the bone tissue in the presence of Al³⁺. In contrast, it was found that Zn²⁺ ions may act as a protective agent against Al³⁺-induced contamination.     

卡尔曼滤波-分光光度法同时测定长江、嘉陵江地表水中微量铜、镉、锌和铅

以2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚为螯合剂,三氯甲烷为萃取剂,采用卡尔曼滤波和分光光度法同时分析长江和嘉陵江现场采集的地表水样中Cu~(2 ),Cd~(2 ),Zn~(2 )和Pb~(2 )的浓度.4种金属离子的实验室回收率在91.0%-113.1%之间;比较长江、嘉陵江国控点例行监测数据,本方法具有较好的可比性和可靠性,能直接应用于江河水样多种金属污染物的同时定量分析.