Flow-through voltammetry (FTV) with the hanging mercury drop electrode (HMDE)

A flow-through cell with integrated hanging mercury drop electrode for voltammetric, inverse voltammetric, adsorptive voltammetric, and chronoamperometric methods is described. HMDE droplets are automatically formed and renewed. By optimizing the flow-channel the sensitivity could be increased approximately five times in comparison with batch methods using the same deposition conditions.Dedicated to Professor Dr. Rolf Neeb on the occasion of his 65th birthday     

A flow-through cell for differential pulse anodic stripping voltammetry

A flow-through voltammetric cell with a hanging mercury drop electrode has been developed to fit the static mercury drop electrode (PAR 303). The design has resulted in a linear increase of sensitivity with flow rate and an enhancement of sensitivity by the wall-jet effect. The cell is used in a flow injection system in which samples are introduced with a R??i?ka—Hansen injector. The mercury drop is held at plating potentials while the sample peak passes through the cell. Stripping is done under stopped flow conditions, to reduce noise, after the sample has been washed completely from the cell. The stripping thus takes place into the carrier electrolyte which always has a constant composition independent of sample constituents. Film-forming interfering species will, however, remain on the surface of the mercury drop. The effect of medium exchange on films produced by l-cysteine is reported. The flow-through medium exchange simplifies deaeration, speeds up analysis and reduces contamination.     

Bismuth Film Voltammetric Sensor on Pyrolyzed Photoresist/Alumina Support for Determination of Heavy Metals

Voltammetric sensors based on bismuth film electrodes are an attractive alternative to other sensors for application in electroanalysis of heavy metals. Bismuth film electrodes can be formed by a similar method on the same substrates as mercury. These systems were used most frequently for simultaneous determination of heavy metals such as Pb, Cd and Zn by anodic stripping voltammetry. Our voltammetric sensor was fabricated on an alumina substrate. A photoresist film prepared by pyrolysis of positive photoresist S‐1813 SP15 on the alumina substrate was used as an electrode support for bismuth film deposition. The influence of the Nafion membrane on the measurement sensitivity of the sensor and mechanical stability of the bismuth film were investigated. The sensor was successfully applied for determination of Pb, Cd and Zn in an aqueous solution in the concentration range of 0.2 to 10 µg L^?1 by square wave anodic stripping voltammetry on an in‐situ formed bismuth film electrode with Nafion‐coating. Parameters of the sensor such as sensitivity, linearity, detection limit, repeatability and life‐time were evaluated. In the best case, the detection limits were estimated as 0.07, 0.11 and 0.63 µg L^?1 for Pb, Cd and Zn, respectively. Finally, the applicability of the sensor was tested in analysis of Pb, Cd and Zn in real samples of tap and river water using the method of standard additions.     

Preparation of a gold electrode modified with tri-n-octylphosphine oxide and its application to determination of mercury in the environment

A gold film electrode modified with a film of tri-n-octylphosphine oxide (TOPO) in a PVC matrix has been prepared and tested. Cyclic voltammetric experiments have shown that the electrode is useful for highly selective voltammetric determinations of a number of metals, primarily Hg, Cr, Fe, Bi, Sb, U and Pb. The electrode has been applied to the anodic stripping voltammetric determination of mercury in some environmental samples, such as river sediments. Concentrations of 0.02-50 ppm of mercury can be determined with good precision and accuracy, as demonstrated by analyses of reference materials. A selective decomposition of the samples at laboratory temperature decreases the danger of sample contamination and of volatilization of mercury.     

Determination of mercury in aquatic ecosystems

Small concentrations of mercury are determined by the example of the quantitative recovery of a toxicant from snow water in a segregating system with no organic solvent (water-antipyrine-sulfosalicic acid). The organic component of the system in situ forming as a result of acid-base interactions was used in microliter amounts to modify a graphite indicator electrode and register an analytical signal of mercury. The reliability of the results of voltammetric determination was checked by the independent cold vapor method. Organic components obtained by segregation were used to extract mercury from the conservative ecosystem component, solid snow particles, snow water preconcentrated with a membrane filter, river suspensions from surface water and floodplain soils, and also fish samples. The characteristic features of mercury extraction with a mixture if mineral acids and the liquid organic component of a segregating system with no organic solvent are discussed.     

Development of an amperometric biosensor based on acetylcholine esterase covalently bound to a new support material

A new type of amperometric biosensor based on immobilised acetylcholine esterase was designed and constructed. The enzyme was immobilised on a flow-through working electrode, which was prepared from reticulated vitreous carbon (RVC) or from a composite material consisting of RVC and superporous agarose. The sensor was operated in FIA mode using acetylthiocholine as a substrate. The sensor responded to inhibitors such as paraoxon-10(-9) mol was detected by the sensor in a non-optimised configuration. The practical lifetime of the sensor was at least 1 month.     

Stripping Analysis of Trace Metals at a Flow-Through Reticulated Vitreous Carbon Electrode after the Preconcentration by Supported Liquid Membrane Technique

Abstract

The performance of a flow-through mercury coated reticulated vitreous carbon (RVC) electrode in the potentiometric stripping analysis (PSA) of trace metals has been examined. A wall-jet glassy carbon cell was used for the comparative experiments. Experimental parameters influencing the stripping signals have been optimised in order to use the stripping analysis after the preconcentration and matrix isolation by supported liquid membrane (SLM) technique. The SLM with di-2-ethylhexyl-phosphoric acid (DEHPA) as the extractant in the membrane liquid for proton driven transport of trace metals across the membrane has been chosen. Results presented for lead determination in river water demonstrate the analytical advantages of coupled technique SLM-PSA.     

The online removal of dissolved oxygen from aqueous solutions used in voltammetric techniques by the chromatomembrane method

The applicability of the chromatomembrane method for the removal of dissolved oxygen from solvents used in voltammetric measurements was investigated. The chromatomembrane cell combined with a flow-through system allows an online deaeration of solutions. These experiments employed a mercury film electrode as working electrode and differential pulse anodic stripping voltammetry as the measuring method. Different eluents with adequate supporting electrolyte (without analyte) were measured to determine the background current, whether any contribution of oxygen is detectable. Voltammograms of eluents deaerated with the chromatomembrane method are compared to those of eluents purged with nitrogen for several minutes immediately before the measurement. No differences in the background currents can be observed when defined flow rates of eluent and nitrogen are maintained. Determinations of cadmium and lead even indicate the high efficiency of this method.     

Differential pulse voltammetric determination of selected nitrophenols on novel type of porous silver working electrode prepared by powder metallurgy

Nitrophenols are important environmental pollutants and their monitoring is important because of their genotoxic and ecotoxic properties. Easy electrochemical reduction of nitro groups can be used for their voltammetric determination using mercury based electrodes. However, requirements of green analytical chemistry prompted us to investigate a novel type of silver porous electrode (AgPE) prepared by powder metallurgy compatible with both “green” and “white” analytical chemistry requirements. In this paper, AgPE was for the first time successfully used for differential pulse voltammetric determination of micromolar concentrations of 2-nitrophenol (NP), 2,4-dinitrophenol (DNP), and 2,4,6-trinitrophenol (TNP) in aqueous media. The main advantage of the novel method is the possibility to use small sample volume (down to 25 μL) and to work in the presence of oxygen when using supporting electrolyte of pH 3. This advantage partially compensates the fact that the obtained sensitivity and limit of detection are not better than with the previously investigated electrodes.     

In situ voltammetric measurement of trace elements in lakes and oceans

A submersible probe with a flow-through cell allowing in situ voltammetric measurements by means of either a mercury film or a mercury drop electrode has been developed. The various possibilities of voltammetric measurements in the presence of dissolved oxygen have been reviewed and tested. Optimum conditions for the determination of trace metals in oxygenated waters have been found. In situ determinations of Mn(II) in anoxic lake water and of trace metals (Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺) in oxygen-saturated sea water are reported.     

Determination of N-acetyl-L-cysteine by flow-injection potentiometry

A multi-purpose tubular flow-through sensor was constructed with an AgI-based membrane. The membrane was prepared by pressing silver salts (AgI, Ag₂S) and powdered Teflon. This membrane was incorporated in the tubular flow-through sensor body. A 2-mm diameter hole was drilled through the center of the tubular sensor and the membrane, thus determining the active sensor volume of about 4 μL. The tubular sensor with reference electrode was placed into a complex flow-injection system and used for the flow-through determination of N-acetyl-L-cysteine, (NAC), in perchloric acid medium, pH = l. Linear dependence was established between the recorded signal height and the concentration of NAC in the injected sample. The recorded change in potential for a decade change in concentration, 62 mV {p (NAC)}^–1, in the concentration range from 1 × 10^–4 to 1 × 10^–1 mol L^–1, was based on the formation mechanism of the sparingly soluble deposit between silver and NAC on the surface of the sensitive part of the membrane. Received: 7 July 1997 / Revised: 22 September 1997 / Accepted: 26 September 1997     

Voltammetric analysis using a self-renewable non-mercury electrode

Galinstan is a new kind of electrode material and the galinstan electrode is a promising alternative to the commonly used mercury electrodes. The eutectic mixture of gallium, indium and tin is liquid at room temperature (m.p. −19°C) and its voltammetric behaviour is similar to that of mercury. The potential windows of use were determined for different pH values and are similar to those obtained with conventional mercury electrodes. Furthermore, the high hydrogen overpotential, which is characteristic for mercury, can be observed when galinstan is used as electrode material. Galinstan can be employed as a liquid electrode in the voltammetric analysis of different metal ions, such as lead and cadmium, in different supporting electrolytes. Our results indicate that the non-toxic liquid alloy galinstan could therefore become immensely important in electrochemical research as a potential surrogate material for mercury.     

Photo-switchable ion and enzyme sensors. Photoinduced potentiometric response of glassy carbon electrode coated with polymer or polymer/enzyme dual membrane

Photo-switchable ion and enzyme sensors were fabricated by the use of glassy carbon electrode coated with nonactindoped or enzyme modified poly(vinyl chloride) (PVC) membranes. The ion sensor with nonactin-doped PVC membrane, which contained spirobenzopyran as the photosensitive dye, exhibited a potentiometric photoresponse to NH4+ ion in the solution. The dynamic range of the NH4+ ion sensor was 10(-7)--10(-3) M. Urea, adenosine, and asparagine sensors were prepared by coating the surface of the NH4+-ion sensor with urease, adenosine deaminase, and asparaginase membranes, respectively. These enzyme sensors could be used for determining the substrates at the micro mole level. The performance characteristics of these sensors were compared with those previously prepared membrane electrode sensors.     

Mercury(II) ion-selective polymeric membrane sensor based on a recently synthesized Schiff base

A new polyvinyl chloride (PVC) membrane electrode that is highly selective to Hg(II) ions was prepared by using bis[5-((4-nitrophenyl)azo salicylaldehyde)] (BNAS) as a suitable neutral carrier. The sensor exhibits a Nernstian response for mercury ions over a wide concentration range (5.0×10⁻²-7.0×10⁻⁷ M) with a slope of 30±1 mV per decade. It has a response time of <10 s and can be used for at least 3 months without any measurable divergence in potential. The electrode can be used in the pH range from 1.0 to 3.5. The proposed sensor shows fairly good discriminating ability towards Hg²⁺ ion in comparison with some hard and soft metals. The electrode was used in the direct determination of Hg²⁺ in aqueous solution and as an indicator electrode in potentiometric titration of mercury ions.     

HPLC online reductive scanning voltammetric detection of diquat, paraquat and difenzoquat with mercury electrodes

To establish an electrochemical HPLC detection system which is suitable for the voltammetric characterisation of unknown contaminants and food components at working potentials lower than –1 V, a modified flow-through cell for the use of a hanging mercury drop electrode (HMDE) is described. The introduction of silanised glass capillaries and a new flow-channel design provide a high HMDE lifetime, which is recommended in HPLC detection. As test system the herbicides diquat, paraquat and difenzoquat and ethylviologen as internal standard were measured using differential pulse voltammetry (DPV) detection to improve selectivity. Spiked water samples were analysed with voltammetric and UV-detection and results agreed well.     

Mercury(II) ion-selective electrodes based on p-tert-butyl calix[4]crowns with imine units.

A PVC membrane incorporating p-tert-butyl calix[4]crown with imine units as an ionophore was prepared and used in an ion-selective electrode for the determination of mercury(II) ions. An electrode based on this ionophore showed a good potentiometric response for mercury(II) ions over a wide concentration range of 5.0 x 10(-5) - 1.0 x 10(-1) M with a near-Nernstian slope of 27.3 mV per decade. The detection limit of the electrode was 2.24 x 10(-5) M and the electrode worked well in the pH range of 1.3 - 4.0. The electrode showed a short response time of less than 20 s. The electrode also showed better selectivity for mercury(II) ions over many of the alkali (Na+, -1.69; K+, -1.54), alkaline-earth (Ca2+, -3.30; Ba2+, -3.32), and heavy metal ions (Co2+, -3.67; Ni2+, -3.43; Pb2+, -3.31; Fe3+, -1.82). Ag+ ion was found to be the strongest interfering ion. Also, sharp end points were obtained when the sensor was used as an indicator electrode for the potentiometric titration of mercury(II) ions with iodide and dichromate ions.     

Electrochemical reduction of selenium on a silver electrode and its determination in river water

A new, simple, and fast method is described for determining selenium based on a silver wire electrode flow-through voltammetric detector. A comparison was done between the sensitivity of disk silver, mercury-modified glassy carbon, and mercury-modified gold electrodes. The response of the flow-through voltammetric detector was evaluated with respect to each electrode’s operating potential and pH in direct current mode. The limit of detection (3s) for Se(IV) was below 0.01 mg/L. The flow-through system does not need deposition times and the organic matter does not need to be removed before determining selenium in river water.     

环糊精聚合物与苯醌的分子包合作用及其在酶电极中的应用

研究了水溶性环糊精预聚合物的存在对苯醌/氢醌体系在铂电极上氧化还原行为的影响, 根据伏安曲线讨论了该预聚合物与苯醌的分子包合作用。环糊精预聚合物与戊二醛缩聚反应而形成的不溶性聚合物膜用于葡萄糖氧化酶的固定化, 以制得新型的第二代葡萄糖电极。由于分子包合作用, 作为电子受体的苯醌在含酶的环糊精聚合物膜中具有较高的浓度, 从而加速了固定化酶的电子传递。测定了酶电极上BQ反应的动力学参数。     

Polarography��past, present, and future

Polarography was first developed as an automated method of voltage-controlled electrolysis with dropping mercury electrode. The spontaneously renewed pure electrode surface provided reproducible electrochemical results which enabled scientists to work out adequate theory and rich analytical applications. The original method was then instrumentally modified in various ways. Later, hanging mercury drop was added as an alternative indicator electrode??in this way, polarography turned formally into voltammetry with mercury drop electrodes. Beside, in potential-controlled electrolysis, the mercury drop electrodes have been also used in current-controlled electrolysis (chronopotentiometry)??there, it has provided new experimental effects. Polarography has thus gradually covered a wide field of electrolytic methods based on the use of mercury electrodes, in which it continues developing.     

Analytical procedure for the simultaneous voltammetric determination of toxic metals in dialysis fluids

A new analytical voltammetric procedure for the simultaneous determination of copper(II), lead(II), cadmium(II), zinc(II), chromium(VI), and manganese(II) in two kinds of dialysis fluid (peritoneal and haemodialysis fluids) is described. The voltammetric measurements were performed using, as working electrode, a stationary mercury electrode, and a platinum electrode and a Agmid R:AgClmid R:KCl ((sat.)) electrode as auxiliary and reference electrodes, respectively, employing 0.1 mol L(-1) dibasic ammonium citrate solution pH 6.9 as supporting electrolyte. For all the elements, the accuracy, expressed as relative recovery R%, was very satisfactory being in the range 94-105%, the precision, expressed as relative standard deviation s(r)%, was lower than 6%, while the limits of detection were of the order of a few units of microg L(-1). The analytical voltammetric procedure has been validated by comparison with spectroscopic (graphite furnace atomic absorption spectroscopy, GFAAS) measurements.