Speciation studies of nickel and chromium in wastewater from an electroplating plant

A speciation scheme involving the use of flame atomic absorption spectrometry (FAAS) and differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV) techniques was applied to studies of nickel and chromium in wastewater from a nickel-chrome electroplating plant. Dimethylglyoxime (DMG) and diethylenetriaminepentaacetic acid (DTPA) were employed as complexing agents for adsorptive voltammetric determination of Ni and Cr, respectively. Cr(III) and Cr(VI) were determined by exploiting differences in their reactivity towards DTPA at HMDE. Total dissolved metal content was in the range 2906-3141 and 30.7-31.2 mg l⁻¹ for Ni and Cr, respectively. A higher percentage of the metal was present as labile species (mean value of 67.9% for Ni and 79.8% for Cr) suggesting that strongly binding ligands are not ubiquitous in the sample. About 77.8% of Cr was found to exist in the higher oxidization state, Cr(IV). Results on effect of dilution on lability of the metal forms in the sample using DPAdCSV showed slight peak shifts to a more negative (cathodic) value by −0.036 V for Ni and −0.180 V for Cr with a dilution factor of 100, while peak intensity (cathodic current) remained fairly constant.     

Ionic Liquid–Liquid Extraction and Supported Liquid Membrane Analysis of Lipophilic Wood Extractives from Dissolving-Grade Pulp

In this study, the extraction of lipophilic wood extractives from dissolving pulp samples using ionic liquid–liquid extraction and a two phase hollow fibre supported liquid membrane was investigated. Ionic liquids are capable of dissolving a range of organic and polymeric compounds and are biodegradable, with a negligible vapour pressure. Pulp samples were dissolved in a suitable amount of molten 1-butyl-3-methylimidazolium chloride to give 5 % cellulose solution. Pure cellulose was regenerated by adding water and filtered off. The ionic liquid-aqueous filtrate was first extracted for lipophilic extractives using liquid–liquid extraction. Then, a two phase hollow fibre supported liquid membrane extraction of lipophilic extractives was performed to extract the derivatized compounds prior to analysis by gas chromatography mass spectrometry. The operational parameters of this sample preparation approach were optimised using sterols and fatty acid methyl esters. The variation of enrichment factors and extraction efficiency with respect to liquid membrane, extraction time, stirring speed and sample pH were observed and used to get the optimal parameters. The approach was used in the analysis of oxygen bleached dissolving pulp samples in which main compounds identified were fatty acids, sterols, fatty alcohols, steroid hydrocarbons and ketones. These compounds were similar to those obtained using molecular solvent extraction method, which indicated the absence of chemical reaction between extractives and ionic liquid used.

     

一些二茂铁苯基亚胺化合物的合成与表征

通过回流对应的二茂铁苯胺和芳香醛的混合物的同样路径合成了一系列新颖的二茂铁苯基亚胺化合物(5~12)。当暴露于空气时化合物5~12稳定,不发生任何分解。所有化合物均用¹H、¹³C NMR,MS,IR,UV-Vis和元素分析表征。还报导了化合物N-(3-bromo-2-hydroxylbenzylidene)-4-ferrocenylimine(10)的单晶结构,其结晶属单斜晶系P2₁/c空间群。     

Pre-concentration of trace elements in short chain alcohols using different commercial cation exchange resins prior to inductively coupled plasma-optical emission spectrometric detection

Chelex-100, Dowex 50W-x8 and Dowex MAC-3 exchange resins were investigated for separation and pre-concentration of trace amounts of Cd, Cr, Cu, Fe, Mn, Pb, Ti and Zn in alcohols with respect to retention and desorption characteristics. Dowex 50W-x8 was found to be the best sorbent with percentages recoveries >95%. In addition, Chelex-100 appeared to be suitable for the pre-concentration of Cu, Fe and Zn, whereas Dowex MAC-3 was selective for Cu and Fe. Therefore, Dowex 50W-x8 was used for further investigations. The relative standard deviations <4% (n = 20), limits of detection and quantification were 0.1–1.2 μg L⁻¹ and 0.3–1.5 μg L⁻¹, respectively. The SPE method was validated against a certified reference material and the results were in agreement with certified values. The accuracy of the optimized method was verified by the recovery test in the spiked alcohol samples. The accuracy and spike recovery test for different metal ions were in the range 98–102% and 95–105%, respectively. The optimized method was applied to the separation and pre-concentration of metal ions in different commercial alcohol samples.     

Studies of difurylmethane‐maleic anhydride copolymer as an ion‐responsive membrane for the determination of mono‐, di‐ and tri‐valent cations

The synthesis of the difurylmethane‐maleicanhydride(DFM‐MAH) copolymer was done by reacting difurylmethane with maleic acid followed by hydrolysis with sodium hydroxide to produce the anhydride sodium salt. Construction of a sensor with the copolymer as the ion‐exchanger material was done by mixing the copolymer with poly(vinylchloride), PVC, plastic matrix and dibutylphthalate (DBP) plasticizer in tetrahydrofuran (THF) solvent to form a paste. The paste was coated on a piece of silver wire to produce a coated wire electrode (CWE). The response characteristics of the copolymer‐CWE, in potentiometric analysis, were studied for mono‐, di‐ and tri‐valent cations. All the cations studied showed a near‐Nernstian response for concentrations ranging from 5 x 10⁻⁸ M to 1 x 10⁰M in triethanolamine buffer in aqueous media (0.5 M, pH 10.5). The membrane had a composition of 20:20:60 for the copolymer, PVC and DBP.     

Voltammetric detection of sulfonamides at a poly(3-methylthiophene) electrode

Detection of sulfonamide compounds in a mixture of standards at a poly(3-methylthiophene) coated on glassy carbon (GC) electrode is reported. The polymer, poly(3-methylthiophene), was electrochemically synthesized at a GC rotating disk-working electrode versus Ag/AgCl using cyclic voltammetry (+0.5 to +2.0 V). Square wave voltammetry (SQWV) with cathodic reduction (0 to -4.0 V) was used for the detection of seven sulfonamide compounds in a mixture. The working concentration ranges (curvilinear) established for different compounds in Britton-Robinson (BR) buffer (pH 6.26), were: 5.0x10(-6)-3.2x10(-3) M sulfamerazine, 5.0x10(-6)-3.2x10(-3) M sulfadiazine, 7.5x10(-7)-3.2x10(-4) M sulfasalazine, 9.0x10(-7)-5.0x10(-4) M sulfamethazine, 6.5x10(-8)-3.5.0x10(-5) M sulfamethoxazole, 9.7x10(-8)-5.0x10(-5) M sulfathiazole, and 9.0x10(-8)-3.2x10(-5) M 5-sulfaminouracil. Detection limits were calculated as: 3.9x10(-6) M for sulfamerazine; 4.0x10(-6) M sulfadiazine; 2.5x10(-7) M sulfasalazine; 3.7x10(-7) M sulfamethazine; 4.0x10(-8) M sulfamethoxazole; 6.4x10(-8) M sulfathiazole and 6.0x10(-9) M 5-sulfaminouracil. The data suggests a potential application of the poly(3-methylthiophene) (P3MT) electrode for determination of sulfonamides in veterinary and other applications.     

Modelling of the impedimetric responses of an aflatoxin B1 immunosensor prepared on an electrosynthetic polyaniline platform

Aflatoxins are a group of mycotoxins that have deleterious effects on humans and are produced during fungal infection of plants or plant products. An electrochemical immunosensor for the determination of aflatoxin B₁ (AFB₁) was developed with AFB₁antibody (AFB₁-Ab) immobilized on Pt electrodes modified with polyaniline (PANi) and polystyrene sulphonic acid (PSSA). Impedimetric analysis shows that the electron transfer resistances of the Pt/PANi–PSSA electrode, the Pt/PANi–PSSA/AFB₁-Ab immunosensor and Pt/PANi–PSSA/AFB₁-Ab incubated in bovine serum albumin (BSA) were 0.458, 720 and 1,066 kΩ, respectively. These results indicate that electrochemical impedance spectroscopy (EIS) is a suitable method for monitoring the change in electron transfer resistance associated with the immobilization of the antibody. Modelling of EIS data gave equivalent circuits which showed that the electron transfer resistance increased from 0.458 kΩ for the Pt/PANi–PSSA electrode to 1,066 kΩ for the Pt/PANi–PSSA/AFB₁-Ab immunosensor, indicating that immobilization of the antibody and incubation in BSA introduced an electron transfer barrier. The AFB₁ immunosensor had a detection limit of 0.1 mg/L and a sensitivity of 869.6 kΩ L/mg.     

Characterization and stability of TiO2 nanoparticles in industrial dye stuff effluent

Stability studies were conducted in different solutions (deionized water (DI), NaCl, CaCl₂, and MgCl₂) at different pH. Agglomeration and zeta potential were influenced by ionic strength, type of electrolyte, and the presence of dye stuff. The Derjaguin–Landau–Verwey–Overbeek (DLVO) theory was used to analyze the stability and/or agglomeration of the nanoparticles in the different solutions. Repulsive or attractive forces stipulated by the DLVO theory were used to quantitatively discuss the results. The increase in ionic strength increased agglomeration which was linked to pH_pzc, as there were minimal electrostatic repulsions at the pzc, yet the attractive van der Waals forces were dominant. Addition of the dye stuff significantly decreased the agglomeration as the dye stuff changed the overall zeta potential of TiO₂ nanoparticles to negative across the entire pH which improved stability as there were particle–particle repulsions. Monovalent and divalent cations were compared and Ca²⁺ increased the mean diameter of nanoparticles as it effectively decreased the EDL of the nanoparticles, thus enhancing agglomeration. The DLVO theory was successful at explaining, in terms of the interaction energies between nanoparticles, the phenomena that caused either agglomeration or stability of the as-synthesized TiO₂ nanoparticles in the different solutions.     

Solid-phase extraction of Zn(II), Cu(II), Ni(II) and Pb(II) on poly(vinyl chloride) modified with 3-ferrocenyl-3-hydroxydithioacrylic acid, and their subsequent determination by electrothermal atomic absorption spectrometry

A new chelating resin based on poly(vinyl chloride) functionalized with 3-ferrocenyl-3-hydroxydithioacrylic acid has been synthesized and characterized. The resin was used as a packing material in an off-line mini-column solid-phase extraction system for preconcentration of Zn, Ni, Cu and Pb in water samples prior to their determination using electrothermal atomic absorption spectrometry. Analytical parameters such as pH, flow rate and sample breakthrough volume were optimized. The breakthrough volume for 0.2 μg of analyte using 0.1 g of adsorbent was 60–100 mL, permitting enrichment factors of at least 60. The proposed procedure, validated using a riverine water reference material (SLRS-3), was applied to environmental water samples. The potential for use of the chelating resin to separate interfering ions such as Na, K, Mg and Ca is also explored. Correspondence: Jackson K. Kiptoo, Department of Chemistry, Jomo Kenyatta University of Agriculture and Technology, P.O. Box 62000-00200, Nairobi, Kenya     

一些二茂铁苯基亚胺化合物的合成与表征

通过回流对应的二茂铁苯胺和芳香醛的混合物的同样路径合成了一系列新颖的二茂铁苯基亚胺化合物(5~12)。当暴露于空气时化合物5~12稳定,不发生任何分解。所有化合物均用¹H、¹³C NMR,MS,IR,UV-Vis和元素分析表征。还报导了化合物N-(3-bromo-2-hydroxylbenzylidene)-4-ferrocenylimine(10)的单晶结构,其结晶属单斜晶系P2₁/c空间群。