Hg (II) extraction in a PEG-based aqueous two-phase system in the presence of halide ions. I. Liquid phase analysis

The partition behaviour of Hg (II) was studied in an aqueous polyethylene glycol (PEG) — (NH₄)₂SO₄ two-phase system as a function of halide, halide concentration, and pH. For a system prepared by mixing equal volumes of 40 % (w/w) PEG (1550) with 40 % (w/w) (NH₄)₂SO₄, Hg(II) remains almost exclusively in the salt-rich phase. The addition of NaX (X = Cl⁻, Br⁻, I⁻) enhances Hg (II) partition into the PEG-rich phase due to the formation of halide complexes. The efficiency of halide extractants increases in the order: Cl⁻ < Br⁻ < I⁻. Mercury extraction is improved at lower halide ion concentration by higher stock salt solution acidity. From the distribution coefficients determined as a function of halide ion concentration, the extracted species were identified. The Hg (II) extractability is determined by the type and stability of the Hg (II) halide species, and depends on the stock salt solution acidity. The observed behaviour is discussed and a possible extraction mechanism is proposed.     

Cd(II) determination in the presence of aqueous micellar solutions

The equilibrium constants and molar absorptivities for the fast formation of a 1:3 complex between cadmium(II) (Cd(II)) and dithizonate anion, in the presence of cationic and non-ionic surfactants, allowed a simple and fast spectrophotometric determination of total cadmium. Indeed, the molar absorptivities of the Cd(II)-dithizone (Dz) complex formed in the presence of the neutral Triton X-100 and cationic cetyltrimethylammonium bromide (CTAB) surfactants are almost twice the value observed in the standard method and the maxima of absorption are shifted by about 40 nm when compared with the standard method. Clearly, the use of neutral and cationic surfactants promotes a higher value of the molar absorptivities of the complex, resulting in an increase in the sensitivity of the method. Application of the method to the desorption of Cd(II) ions from clays is illustrated.     

聚乙二醇-硫酸铵双水相萃取次甲基蓝的研究

利用分光光度法研究了次甲基蓝在聚乙二醇-硫酸铵双水相体系的萃取行为,探索了质量配比(mPEc/m(NH4)2SO4)、温度和次甲基蓝的浓度对双水相及次甲基蓝萃取率(Y)的影响.实验表明:(1)在一定的温度和浓度下,随着mPEC/m(NH4)2SO4的减小,分配系数K( cup/clow)增加,萃取率Y略有减小;(2)在一定的质量配比和浓度下,分配系数K(cup/clow)随温度的升高而增大,但萃取率Y却基本保持不变;(3)在一定的质量配比和温度下,随着次甲基蓝浓度的增加,分配系数K(cup/clow)增大;萃取率Y略有增加.在mPEG/m( NH4) 2SO4为1.50∶1,c次甲基蓝=8.915×10-5mol/L、t=30℃的实验条件下,K(cup/clow)=22.14,萃取率(y)可达95.43％.     

Preparation and characterization of magnetic bioadsorbent for adsorption of Cd(II) ions

A facile magnetic chitosan composite used for heavy metal ions removal was prepared. The adsorbents with large specific area and rich carboxyl groups exhibited good removal of Cd(II) ions and could be easily separated with magnetic separation. The adsorption capacity of Cd(II) was 48 ​mg ​g⁻¹ and the removal efficiency reached 86.7% after five cycles. Thus, the prepared magnetic chitosan composite could act as a potential adsorbent for Cd(II) ions removal.     

Solid-phase extraction and preconcentration of cadmium(II) in aqueous solution with Cd(II)-imprinted resin (poly-Cd(II)-DAAB-VP) packed columns

A novel chelating resin (poly-Cd(II)-DAAB-VP) was prepared by metal ion imprinted polymer (MIIP) technique. The resin was obtained by one pot reaction of Cd(II)-diazoaminobenzene-vinylpyridine with cross-linker ethyleneglycoldimethacrylate (EGDMA). Comparing with non-imprinted resin, the poly-Cd(II)-DAAB-VP has higher adsorption capacity and selectivity for Cd(II). The distribution ratio (D) values for the Cd(II)-imprinted resin show increase for Cd(II) with respect to both D values of Zn(II), Cu(II), Hg(II) and non-imprinted resin. The relatively selective factor (α_r) values of Cd(II)/Cu(II), Cd(II)/Zn(II) and Cd(II)/Hg(II), are 51.2, 45.6, and 85.4, which are greater than 1. poly-Cd(II)-DAAB-VP can be used at least 20 times without considerable loss of adsorption capacity. Based on poly-Cd(II)-DAAB-VP packed columns, a highly selective solid-phase extraction (SPE) and preconcentration method for Cd(II) from aqueous solution was developed. The MIIP-SPE preconcentration procedure showed a linear calibration curve within concentration range from 0.093 to 30 μg l⁻¹. The detection limit and quantification limit were 0.093 and 0.21 μg l⁻¹ (3σ) for flame atomic absorption spectrometry (FAAS). The relative standard deviation of the eleven replicate determinations was 3.7% for the determination of 10 μg of Cd(II) in 100 ml water sample. Determination of Cd(II) in certified river sediment sample (GBW 08301) demonstrated that the interfering matrix had been almost removed during preconcentration. The column was good enough for Cd(II) determination in matrixes containing components with similar chemical property such as Cu(II), Zn(II) and Hg(II).     

Complexation of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid with Cd(II), Hg(II) and Pb(II) ions in aqueous solution

The persistence of widely used chelating agents EDTA and DTPA in nature has been of concern and there is a need for ligands to replace them. In a search for environmentally friendly metal chelating ligands for industrial applications, complex formation equilibria of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid (BCA6) with Cd(II), Hg(II) and Pb(II) in aqueous 0.1 M NaNO₃ solution were studied at 25°C by potentiometric titration. Complexation was modeled and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions, stable ML^4? complexes dominated the complex formation. The stabilities of Cd(II), Hg(II) and Pb(II) chelates of BCA6 are remarkably lower than those of EDTA and DTPA. Environmental advantages of the use of BCA6 instead of EDTA and DTPA are better biodegradability and lower nitrogen content with a possibility to save chemicals and process steps in pulp bleaching.     

Preparation and characterization of Mg(II)-, Ca(II) and Cd(II) complexes of 1,2-ethanediol and water

Mixed ligand complexes of different compositions were prepared with water, sulfate ion and 1,2-ethanediol as ligand. IR spectra and the thermoanalytical curves of the complexes were recorded. Oxygen atoms bound by one or two coordinate bonds to the metal ion, or by hydrogen-bonds in the crystal, were observed. As for the water molecule, 1,2-ethanediol molecules of crystal and monohydrate type were found, depending on the type of binding of the oxygen atoms.This revised version was published online in November 2005 with corrections to the Cover Date.     

壳聚糖对Cd2+的吸附性能

壳聚糖(ｃｈｉｔｏｓａｎ,简称ＣＴＳ)是由虾、蟹壳脱钙、蛋白质和脂肪后、经化学改性得到的天然高分子聚合物,分子中存在能与金属离子配位的羟基或氨基,其配合物可作为絮凝剂和螯合吸附剂用于水处理[1 3]及湿法冶金[4]等。本文考察了壳聚糖对Ｃｄ2+的静态吸附性能。1　实验部分1.1　试剂与仪器壳聚糖(浙江玉环县化工厂);硫酸镉、硝酸镉(分析纯,广州化学试剂厂);碳酸镉(化学纯,上海试剂二厂),其余试剂均为分析纯。78 1型磁力加热搅拌器(江苏金坛市恒丰仪器厂),501型超级恒温器(上海实验仪器厂),ｐＨＳ 3型酸度计(上海第二分析仪器厂)。1…     

Selective solid phase extraction of trace cadmium(II) and lead(II) from biological and natural water samples by ofloxacin-modified-silica gel

Ofloxacin was successfully used as a chemical modifier to improve the reactivity of silica gel in terms of selective binding and extraction of heavy metal ions. This new functionalised silica gel (SG-ofloxacin) was as an effective sorbent for the solid-phase extraction (SPE) of Cd(II) and Pb(II) in biological and natural water samples and their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). Experimental conditions for effective adsorption of trace levels of Cd(II) and Pb(II) were optimised with respect to different experimental parameters using the batch and column procedures. The time for 70% sorption for Cd(II) and Pb(II) was less than 2 min. Complete elution of the adsorbed metal ions from the SG-ofloxacin was carried out using 2.0 mL of 0.5 mol L^?1 of HCl. Common coexisting ions did not interfere with the separation and determination at pH 4.0. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.17 and 48.69 mg g^?1 for Cd(II) and Pb(II), respectively. The detection limits of the method were found to be 0.29 and 0.13 ng mL^?1 for Cd(II) and Pb(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was lower than 3.0% (n = 5). The method was applied to the recovery of Cd(II) and Pb(II) from the certified reference material (GBW 08301, river sediment) and to the simultaneous determination of these cations in different water and biological samples with satisfactory results and yielding 100-folds enrichment factor.     

Chemical modification of rose leaf with polypyrrole for the removal of Pb (II) and Cd (II) from aqueous solution

The rose leaf was successfully modified through coating with polypyrrole (PPy) in chemical oxidative route in order to remove Pb(II) and Cd(II) from aqueous media. The rose leaf/polypyrrole (RL/PPy) composites were characterized in terms of morphology, chemical structure, and conductivity properties. The spectrum were obtained from FTIR results which support the formation of RL/PPy composites. FTIR and SEM results indicate that the polypyrrole is completely covered on rose leaf. The conductivity of composite (1.8215 S/cm) was higher than polypyrrole (2.06 × 10^?3 S/cm). The metal removal studies were monitored by Ultraviolet Visible Absorption Spectrometer (UV-Vis). The optimum conditions were detected for adsorption by changing some experimental conditions (such as adsorbent dosage, contact time and stirring speed, initial concentration of the metal solutions and pH). Following the determination of the optimum conditions, the results of the metal removal from wastewater studies were performed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). Under the optimum conditions, the ICP-OES results obtained for waste water showed the useability of composite for the removal of Pb(II) and Cd(II). The Langmuir and Freundlich models are subjected to adsorption datas. The datas fitted better when by using Freundlich model.     

Novel Three-dimensional Sensor for Rapid Detection of Pb(II) and Cd(II) in Edible Mushrooms

A sensing platform was developed based on the molybdenum disulfide-reduced graphene oxide (MoS₂-RGO). The flower-like MoS₂-RGO nanocomposite had a large number of active sites such as oxygen-containing groups and highly reactive sulfur that contributed to the adsorption and preconcentration of heavy metal ions (HMIs). MoS₂-RGO was synthesized by one-step reduction method. Under optimized conditions, the limits of detection (LODs) for Pb(II) and Cd(II) was 0.13 μg/L and 0.59 μg/L with a linear range of 4.1–207.2 μg/L and 2.2–112.4 μg/L, respectively. The modified sensors had been successfully applied to detect Pb(II) and Cd(II) in three kinds of edible mushrooms.     

Synthesis and characterization of novel Cd(II), Zn(II) and Ni(II) complexes with 2-quinolinecarboxaldehyde selenosemicarbazone. Crystal structure of bis(2-quinolinecarboxaldehyde selenosemicarbazonato)nickel(II)

New complexes of Cd(II), Zn(II) and Ni(II) with 2-quinolinecarboxaldehyde selenosemicarbazone (Hqasesc) were synthesized and structurally characterized. The structure of the ligand, Cd(II) and Zn(II) complexes was determined by NMR and IR spectroscopy, elemental microanalysis and molar conductivity measurements. Both complexes occur in solution in two forms, the major tetrahedral and minor octahedral. In the major Cd(II) complex one qasesc⁻ ligand is coordinated as a tridentate, the fourth coordination site being occupied by acetate, while in the major Zn(II) complex two qasesc⁻ ligands are coordinated as bidentates. In both minor complexes two qasesc⁻ ligands are coordinated as tridentates forming the octahedral geometry around the central metal ion. The only paramagnetic complex in the series is Ni(II) complex for which X-ray structure analysis was performed. The complex has the angularly distorted octahedral geometry with two qasesc⁻ ligands coordinated as tridentates, in a similar way as in the minor complexes of Cd(II) and Zn(II).     

Polarographic Determination of the Formation Constants of the Mixed Ligand Complexes of Cd(II) and Pb(II) with Thiosulphate and Halide Ions

The mixed ligand complexes of Cd(II) and Pb(II) with thiosulphate as a primary ligand and chloride, bromide of iodide (individually) as a secondary ligand have been polarographically, investigated at 30°C and at a constant ionic strength of μ = 1.0 M (NaClO₄). Two mixed ligand complexes were formed with the Cd(II) ion: log β₁₂ = 4.77, 5.30 and 6.78 for the chloride, bromide and iodide ions, respectively; and log β₂₁ = 5.36, 5.04 and 6.22 for the same ions. For the Pb(II)-Ts-Cl system, only one mixed ligand complex was formed with a log stability constant log β₂₁ =4.35. For the Pb(II)-Ts-Br system, three mixed ligand complexes are obtained with log β₁₁ = 3.63, log β₁₂ = 4.51 and log β₂₁ = 4.85.     

Structure of iron (II) and cobalt (II) bromide complexes in aqueous solution by X-ray diffraction analysis

Structures of bromo-metal complexes in concentrated aqueous solutions of FeBr₂ and of CoBr₂ were investigated by X-ray diffraction analysis. The complexes possess an octahedral geometry coordinating Br^– along with H₂O ligands. The frequency factors of metal-Br contacts per one atom of metal were 0.325 for the 2.7M (mol-dm^–3) and 0.747 for the 4.5M FeBr₂ solutions, and 0.280 for the 2.8M and 0.595 for the 4.3M CoBr₂ solutions. The frequency factors suggested that the tendency of metal ions to forming monobromo complexes is in the order, Fe>Co>Ni相似文献   

Extraction mechanism of sulfamethoxazole in water samples using aqueous two-phase systems of poly(propylene glycol) and salt

Based on the poly(propylene glycol)₄₀₀ (PPG₄₀₀)–salt aqueous two-phase system (ATPS), a green, economical and effective sample pretreatment technique coupled with high performance liquid chromatography was proposed for the separation and determination of sulfamethoxazole (SMX). The extraction yield of SMX in PPG₄₀₀–salt ATPS is influenced by various factors, including the salt species, the amount of salt, pH, and the temperature. Under the optimum conditions, most of SMX was partitioning into the polymer-rich phase with the average extraction efficiency of 99.2%, which may be attributed to the hydrophobic interaction and salting-out effect. This extraction technique has been successfully applied to the analysis of SMX in real water samples with the recoveries of 96.0–100.6%, the detection limits of 0.1 μg L⁻¹, and the linear ranges of 2.5–250.0 μg L⁻¹.     

Disposable screen-printed sensors modified with bismuth precursor compounds for the rapid voltammetric screening of trace Pb(II) and Cd(II)

In this article, a study of novel screen-printed electrodes bulk-modified with five potential bismuth precursor compounds (bismuth citrate, bismuth titanate, bismuth oxide, bismuth aluminate and bismuth zirconate) is presented for the determination of Cd(II) and Pb(II) by anodic stripping voltammetry. During the electrolytic deposition step, the precursor was reduced and served as the source of bismuth. Different key parameters were investigated in detail such as the nature of the bismuth precursor compound, the precursor content in the carbon ink, the polarisation range of the sensors, the supporting electrolyte, the stripping waveform, the deposition time, the deposition potential and the long-term stability of the sensors under continuous use. Using bismuth citrate as the precursor, the limit of detection was 0.9 μg L⁻¹ for Pb(II) and 1.1 μg L⁻¹ for Cd(II). The reproducibility on the same sensor (expressed as % relative standard deviation, (n = 8)) was 5.4% for Pb(II) and 7.2% for Cd(II) at the 20 μg L⁻¹ level. Finally, the sensors were applied to the determination of Cd(II) and Pb(II) in water samples.     

Stripping Voltammetric Determination of Pb(II) and Cd(II) Based on the Multiwalled Carbon Nanotubes-Nafion-Bismuth Modified Glassy Carbon Electrodes

Abstract

In this work, a new method for the simultaneous determination of Pb(II) and Cd(II) on the multiwalled carbon nanotubes (MWNT)-Nafion-bismuth modified glassy carbon electrode (GCE) using square-wave anodic stripping voltammetry has been studied. Scanning electron microscopy was used to investigate the characteristics of the MWNT-Nafion-bismuth modified GCE. Well-defined sharp stripping peaks were observed in the determination of Pb(II) and Cd(II) simultaneously on this electrode. Under optimized conditions, the lowest detectable concentrations were 50 ng/l for Pb(II) and 80 ng/l for Cd(II) under a 10 min preconcentration. The attractive performances of MWNT-Nafion-bismuth modified GCE demonstrated its application for a simple, rapid, and harmless determination of trace heavy metals.     

Zn(II), Cd(II) and Hg(II) complexes of 8-aminoquinoline.: Structure,spectra and photoluminescence property

The reaction of 8-aminoquinoline (8-aq) with M(NO₃)₂ and M(ClO₄)₂ (where M = Zn, Cd and Hg) has synthesized complexes of the composition [M(8-aq)₂(H₂O)₂](X)₂ (X = NO₃, ClO₄) whereas MCl₂ has isolated M(8-aq)Cl₂ type non-ionic compounds. The reaction of M(OAc)₂, 8-aq and NaN₃/NH₄CNS in a 1:1:2 mole ratio has separated polynuclear complexes of the composition [M(8-aq)(Y)₂]_n (Y = N₃, NCS). The complexes have been characterized by spectroscopic data and have been structurally confirmed by single crystal X-ray diffraction study in some representative cases. The X-ray structure of [Zn(8-aq)₂(H₂O)₂](NO₃)₂ shows C–H–π, and π–π interactions and forms a H-bonded sheet (with interactions between the oxygen of NO₃ and C(9)–H of 8-aq/coordinated H₂O). A novel one-dimensional cadmium(II) azido complex, [Cd(8-aq)(N₃)₂]n (9), in which the azido takes on an end-on (EO) bridging mode, has been synthesized and characterized. The presence of π–π interactions result in a supramolecular two-dimensional behaviour for the structure. The complexes are photoluminescent at room temperature.     

A heteropore covalent organic framework for adsorptive removal of Cd(Ⅱ) from aqueous solutions with high efficiency

A heteropore covalent organic framework(COF) integrating tetraphenylethene skeleton and catechol segment is designed and synthesized.It exhibits extremely high stability in water under different pH conditions,which makes it an excellent material for adsorptive removal of Cd(Ⅱ) from aqueous solutions with very fast adsorption kinetics,high uptake capacity,and good recyclability.     

On the catalytic effect of thiolactams on the electrochemical reduction of Zn(II) ions

Summary The electroeduction of Zn(II) ions in 1M NaClO₄ in the presence of thiolactams has been studied by means of the faradaic impedance method in wide frequency ranges. The standard rate constants are found to be a linear function of the surface excesses of thiolactams. Catalytic activity of thiolactams increases in the following order: thiopyrrolidone, thiopiperidinone, thiocaprolactam; the enthalpies of activation decrease in this order. The differences in the catalytic activity of thiolactams result mainly from the double layer effect.

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Zum katalytischen Effekt von Thiolactamen auf die elektrochemische Reduktion von Zn(II)-Ionen

Zusammenfassung Die Elektroeduktion von Zn(II)-Ionen in 1M NaClO₄ in Gegenwart von Thiolactamen wurde mittels derFaradayschen Impedanzmethode über große Frequenzbereiche untersucht. Die Standardgeschwindigkeitskonstanten sind eine lineare Funktion der Überschußoberfläche der Thiolactame. Deren katalytische Aktivität steigt in der Reihenfolge Thiopyrrolidon — Thiopiperidinon — Thiocaprolactam; die Aktivierungsenthalpien sinken in der angegebenen Reihenfolge. Die Unterschiede in der katalytischen Aktivität der Thiolactame sind hauptsächlich auf den Doppelschichteffekt zurückzuführen.