Determination of nitrate in water with a new construction of ion-selective electrode

A new design of the liquid-state electrode for nitrate ions is proposed. It contains a porous wick soaked with the liquid ion-exchanger, and has no internal reference solution. This electrode was used for nitrate determination of tap water at the level 8–10 p.p.m. The effects of chloride and hydrogencarbonate are eliminated by the addition of silver sulphate and a phosphate buffer, which also maintains constant ionic strength. Precision of a series of measurements is better than 2%, but the results show differences up to 10% compared to the colorimetric brucine procedure.     

Amperometric measurements with ion-selective electrode membranes in a flow system

Calcium and salicylate sensitive electrode membranes based on plasticized PVC were used for selective amperometric detection in a flow injection system. The peak current was found to depend linearly on concentration and the working range extended well below the potentiometric detection limit.Dedicated to Professor W. Simon on the occasion of his 60th birthday     

Optimization of a sodium ion-selective electrode for use in serum measurements

A sodium ion-selective polymeric membrane electrode has been optimized, especially with reference to serum measurements. For a given combination of polymer and ligand, the choice of membrane solvent is critical. Potentiometric measurements and electrodialysis experiments have shown that the dielectric constant and solubility parameter of the solvent influence the electrode selectivities, stability, slope and limit of detection. For use in serum measurements, it is essential to use an appropriate analytical technique, such as Flow Injection Analysis, which permits exposures to serum for only short periods of time.     

Determination of fluazifop-butyl and fluazifop with the use of disposable solid phase extraction columns for selective clean-up and concentration of Soxhlet soil extracts

Summary An analytical procedure based on the solid phase extraction technology has been developed for the clean-up and concentration of Soxhlet soil extracts containing fluazifop-butyl and fluazifop by the use of a phenyl phase cartridge. No liquid-liquid partition has been used; thus the consumption of organic solvents was limited and the use of chlorinated solvents could be avoided. Quantification has been performed by ion-pair HPLC. Despite the large difference in polarity the recoveries of both the compounds from spiked soil samples between 0.1 and 1 g/g was higher than 90%. The solid-phase adsorption technology resulted in a very effective methodology of clean-up in the case of the polar compound fluazifop, for which a second disposable column with a cyanopropyl phase has been used, and was fairly satisfactory for fluazifop-butyl. The detection limits were less than 0.04 g/g and 0.10 g/g, respectively for fluazifop and fluazifop-butyl.     

Use of disposable open tubular ion exchange pre-columns for in-line clean-up of serum and plasma samples prior to capillary electrophoretic analysis of inorganic cations

A simple analytical system using disposable, open-tubular ion exchange clean-up precolumns coupled in-line to capillary electrophoresis for direct injection of biological samples is presented. The clean-up precolumns were prepared from fused silica capillaries by thermally initiated layer-by-layer polymerization of poly(butadiene-maleic acid) (PBMA) directly on the capillary wall. Typically, 6 cm long precolumns with 4-layers of PBMA were used for sample pretreatment. A robust and reproducible coupling between the precolumn (75 μm ID) and the analytical capillary (50 μm ID) was achieved using an inexpensive, commercially available low dead volume union. No extra dispersion of the analyte zones was observed. Proteins and other high molecular weight compounds from biological sample matrices were retained on the cation-exchanger sites of the precolumn, which eliminated their adsorption on analytical capillary walls and ensured stable electroosmotic flow and migration times of target analytes. Unretained small inorganic cations migrated freely into the analytical capillary for separation and detection. Applicability of the sample clean-up procedure was proved by determination of major inorganic cations in blood serum and plasma samples using capillary electrophoresis with contactless conductivity detection. Separations were performed in background electrolyte solution consisting of 15 mM L-arginine, 12.5 mM maleic acid, 3 mM 18-crown-6 at pH 5.5 and repeatabilities of migration times and peak areas were below 1.5% and 7.3%, respectively. Less than 1 μL of biological sample was required for injection.     

离子选择电极阵列土壤中硝态氮测定

土壤硝态氮反映土壤短期氮素供应水平,实时了解土壤硝态氮的含量为精准农业和农业面源污染防控提供支撑,因此,在线实时检测土壤硝态氮方法突破就显得十分迫切。土壤硝态氮中的硝酸根离子在土壤中的高水溶性和流动性为全固态硝酸根离子选择电极高敏感检测土壤中硝态氮提供了条件,固态硝态氮离子选择电极的离子选择膜反应硝酸根离子在被测溶液中的浓度。采用全固态硝酸根离子选择电极,且与温度电极和pH电极融合组成电极阵列对土壤饱和溶液中的硝态根离子进行检测。设计了高输入阻抗运算放大电路对电极信号进行采集,并通过微处理控制蠕动泵完成土壤硝态氮待测溶液连续流动测量及实时传输结果。实验结果表明,电极响应时间≤15 s,斜率-51.63 mV/decade,线性范围10-5-10-2.2 mol/L,最低检测限10-5.23 mol/L。相对标准差在0.78%-4.47%范围内,加标回收率均在90%-110%以内。与国家标准紫外可见分光光度法测试结果相比,相关系数（R2）为0.9952,为土壤硝态氮在现场检测奠定技术基础。     

Metal-modified silica adsorbents for removal of humic substances in water

As novel adsorbents for humic substances, Fe-, Mg-, and Ca-modified silica gels SiO(2)Fe, SiO(2)Mg, and SiO(2)Ca were prepared, and their adsorbabilities to humic and fulvic acids were evaluated in water at 25 degrees C for 20 h. Among these adsorbents, SiO(2)Fe indicated the highest adsorbability, in which removing humic substances in water was accomplished to 80-97%. By calcination at 600 degrees C and washing with water, adsorbabilities of the silica adsorbents deteriorated except for the case of calcination of SiO(2)Ca. This is due to changing metal modification structures and losing chlorine, judging from elemental analysis, TG-DTA, and XPS. Especially, the modifier Fe was tightly fixed on the silica surface of SiO(2)Fe, since the metal content was almost constant even after the calcination and water washing unlike the other adsorbents. Therefore, we found that SiO(2)Fe is the most useful adsorbent among the silica adsorbents and that its modification structure is composed of SiOFe, FeCl, and FeOH. In addition, the adsorption mechanism is explained by an interaction between Fe and humic substance molecule having carboxylate and phenolate groups, accompanied with anion exchange of chloride ion Cl(-) for the humic substance molecule via the silica pores. SiO(2)Fe may be applied to an adsorbent alternative for charcoal in water purification plants, and the used SiO(2)Fe may be further reused as a fertilizer since humic substances have plant-glowing ability and silica strengthens plant parts.     

Use of ethylene-vinyl-acetate as a new membrane matrix for calcium ion-selective electrode preparation

A new polymer matrix based membrane electrode with an ion-exchanger responding to calcium was constructed by dissolving the copolymer ethylene-vinyl-acetate together with the ion-exchanger in chloroform in the presence of a mixture of dioctylphthalate-nitrobenzene as plasticizer. The ion-exchanger used as the electroactive component was calcium didecyl phosphate in di-(n-octylphenyl) phosphonate (Orion). This electrode exhibited near-Nernstian response over the concentration range 10(-1)-4 x 10(-6)M calcium. The pH did not affect the electrode performance within the range 8-11. Response time varied from 15 to 120 sec and the lifetime exceeded six months. The membrane is subject to static charge buildup, but this is avoided by controlling the level of dryness of the membrane. Selectivity coefficients determined for both monovalent and divalent cations showed negligible interference by most of these ions. The electrode was applied successfully to the determination of calcium in commercial mineral waters.     

Use of a crown ether-heteropoly acid precipitate as a potassium ion-selective membrane electrode

Summary A Potassium ion-selective electrode based on dibenzo-18-crown-6-tungstophosphoric acid precipitate membrane is prepared and conditions for the best functioning have been investigated. The working concentration and pH-range of the electrode is 2.0×10^–2 to 1.3×10^–6 mol/l and 2.9–6.5, respectively. The selectivity coefficient values for a large number of cations are quite low except for caesium and ammonium ions. The electrode can tolerate non-aqueous content upto 20%.

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Kaliumion-sensitive Membranelektrode auf Basis von Kronenether-Heteropolysäure

     

Flow-injection determination of phosphate with a cadmium ion-selective electrode

A flow-injection method is described, in which phosphate standards are introduced into a reagent stream containing Cd(2+) ,resulting in the formation of Cd(3)(PO(4))(2). The associated reduction in free metal concentration is sensed by a cadmium-selective electrode. With the exception of major interference from iodide and moderate interference from bromide and thiocyanate, the system exhibits excellent response to phosphate and selectivity over several common anions in solutions buffered at pH 8.4. A maximum sampling rate of 160/hr is possible for phosphate standards in the concentration range 10(-1)-10(-1)M with a 10(-4)M Cd(2+) reagent stream at a total flow-rate (carrier and reagent stream combined) of 8.4 ml/min.     

Use of a bismuth ion-selective electrode for investigation of bismuth complexes of citric and malic acids

A bismuth ion-selective electrode has been used to determine the nature and stability of the complexes formed by bismuth with citric acid and malic acid, by measurement of the response of the electrode to different total bismuth concentrations at various combinations of pH and total ligand concentration. The values found were beta(2) = 3 x 10(13) for Bi(Cit)(2)(3-) and beta(3) = 8 x 10(9) for Bi(Mal)(2)(3-).     

A solid-phase extraction procedure for the clean-up of thiram from aqueous solutions containing high concentrations of humic substances

A simple solid-phase extraction (SPE) procedure with an octadecyl bonded phase silica (C₁₈) was developed for clean-up of the fungicide thiram from aqueous solutions containing high concentrations of humic substances, for future studies of thiram adsorption onto solid humic substances or soils. Suspensions of humic acids and soil, in aqueous 0.01 M CaCl₂ solution, were prepared and used as samples. These extracts were spiked with thiram and immediately applied to a C₁₈-SPE cartridge. Thiram was eluted with chloroform and its concentration measured by spectrophotometry at 283 nm. Non-spiked aqueous extracts (blanks) and a control sample of thiram in 0.01 M CaCl₂ aqueous solution were also prepared and submitted to the same SPE procedure. The results show that humic substances are extensively retained by the C₁₈ cartridge but are not eluted with CHCl₃. Recoveries of 100-104% were obtained for thiram in the presence of humic substances. The SPE procedure described in this work is an efficient clean-up step to remove the interference of humic substances absorbance and to be coupled to any spectrophotometric or HPLC-UV method, usually used for thiram analysis in food extracts.     

Preparation and application of a novel magnetic anion exchange resin for selective nitrate removal

正A novel magnetic anion exchange resin NDM-1 was prepared through suspension polymerization and then functionalized with ammonolysis and alkylating agents.Its application for selective removal of nitrate was performed in comparison with MIEX~.The results demonstrated that NDM-1 achieved higher efficiency in nitrate removal than MIEX~ did,with or without the existence of competing anion SO_4~(2-) ascribed to its longer alkyl chains on exchange sites.Combined with the advantage of easy separation due toγ-Fe_2O_3 implanted,the magnetic anion exchange resin NDM-1 was considered to be superior to MIEX~ for nitrate removal in practical application.     

A cheap alternative to valinomycin for certain analyses with the potassium ion-selective electrode

A pyridine-based macrocylic ionophore containing a 15-membered ring cavity and an octoxy side-chain to confer compatibility with poly(vinyl chloride) is described. This cheap reagent gives a potassium ion-selective PVC membrane electrode which, except for a higher sodium interference, compares well with valinomycin for analyses where the sodium/potassium ratio is ?1. Near-Nernstian response is obtained for 10^?1–10^?5 M potassium ion.     

Use of an ion-selective membrane electrode for the determination of the active components in intestopan

The conditions for the determination of broxyquinoline and brobenzoxaldine, the active components of "Intestopan", by use of ion-selective membrane electrodes are described. Broxyquinoline is determined directly through precipitation with CuSO(4), and brobenzoxaldine is first hydrolysed in alkaline solution and the product precipitated with CuSO(4). In both cases the CuSO(4) in excess is determined by potentiometric titration at pH 5.6 with EDTA, a Cu(2+)-selective electrode being used for end-point detection.     

Determination of tri- and tetravalent ions with a divalent ion-selective electrode

A method of determining tri- and tetravalent ions with a divalent ion-selective electrode is proposed. The determination is based on displacement of the divalent metal ion from the Mg-EDTA or Zn-EDTA complex. The approximate ranges for direct measurement are 3·10^-3–3·10^-4M. Titrimetric methods are recommended for analysis of mixtures of metal ions. Optimal pH ranges and precision are discussed.