Determination of Cu, Pb, Cd, and Zn in river sediment extracts by sequential injection anodic stripping voltammetry with thin mercury film electrode

Determination of Cu, Pb, Cd and Zn was performed in sediment extracts obtained according to the three steps sequential extraction procedure proposed by the European Community Standards, Measurements and Testing Program. The metal content was determined by anodic stripping voltammetry with a thin mercury film electrode controlled by a sequential injection (SIA) system. The proposed method improved the reproducibility of conventional anodic stripping voltammetry, as well as the sample throughput, allowing analysis of 30 to 45 samples per hour. The influence of flow rate and sample volume was studied to achieve an adequate sensitivity for the leachate studied. No interferences due to adsorption of organic matter, colloids, or complexes with slow rate of dissociation were observed. The intermetallic formation of Cu-Zn was avoided by forming the mercury film in presence of Ga(III) ions in the SIA system, resulting in low consumption of reagent in comparison to flow injection or continuous flow systems. Results were in good agreement with those obtained by Induced Coupled Plasma – Atomic Emission Spectroscopy (ICP- AES). Received: 18 October 1999 / Revised: 14 December 1999 / Accepted: 19 December 1999     

Application of sequential injection analysis to anodic stripping voltammetry

Sequential injection analysis (SIA) technique has been applied to anodic stripping voltammetry (ASV). The sample and reagent volumes can easily be controlled by SIA. The technique also allows plating of the mercury film on-line and therefore substantially reduces generation of mercury containing waste. Repeated sample passage through the detector was used during the deposition step to enhance the sensitivity. The way solution handling is done in SIA allows an easy and effective medium exchange procedure increasing the selectivity of the method. This has been demonstrated by changing the stripping medium and having different complexing agents in the stripping solution. The observed potential shifts of the stripping peaks could theoretically be explained in the cases where the complexation constants are known. Calibration and the standard addition methods are discussed and demonstrated by determining copper in tap water as a method of testing the procedure.     

On-line coupling of sequential injection lab-on-valve to differential pulse anodic stripping voltammetry for determination of Pb in water samples

Sequential injection lab-on-valve (LOV) was first proposed for analyzing ultra-trace amounts of Pb using differential pulse anodic stripping voltammetry (DPASV) with a miniaturized electrochemical flow cell fabricated in the LOV unit. Deposition and stripping processes took place between the renewable mercury film carbon paste electrode and sample solution, the peak current was employed as the basis of quantification. The mercury film displayed a long-term stability and reproducibility for at least 50 cycles before next renewal, the properties of integrated miniature LOV unit not only enhanced the automation of the analysis procedure but also declined sample/reagent consumption. Potential factors that affect the present procedure were investigated in detail, i.e., deposition potential, deposition time, electrode renewable procedure and the volume of sample solution. The practical applicability of the present procedure was demonstrated by determination of Pb in environmental water samples.     

Use of a modified, high-sensitivity, anodic stripping voltammetry method for determination of zinc speciation in the North Atlantic Ocean

Zinc speciation is considered to be an important determinant of the biological availability of zinc. Yet in oceanic surface waters, characterization of zinc speciation is difficult due to the low concentrations of this essential micronutrient. In this study, an anodic stripping voltammetry method previously developed for the total determination of cadmium and lead was successfully adapted to the measurement of zinc speciation. The method differs from previous zinc speciation anodic stripping voltammetry methods in that a fresh mercury film is plated with each sample aliquot. The fresh film anodic stripping voltammetry method was compared to competitive ligand exchange cathodic stripping voltammetry in a profile from the North Atlantic Ocean. Results using the fresh film anodic stripping voltammetry method were similar to those determined using the cathodic stripping voltammetry method, though ligand concentrations determined by fresh film anodic stripping voltammetry were generally slightly higher than those determined by cathodic stripping voltammetry. There did not seem to be a systematic difference between methods for the estimates of conditional stability constants. The ligand concentration in the North Atlantic profile ranged from 0.9 to 1.5 nmol L⁻¹ as determined by fresh film anodic stripping voltammetry and 0.6 to 1.3 nmol L⁻¹ as determined by cathodic stripping voltammetry. The conditional stability constants determined by fresh film anodic stripping voltammetry were 10^9.8-10^10.5 and by cathodic stripping voltammetry were 10^9.8-10^11.3.     

Determination of traces of metals by anodic stripping voltammetry at a rotating glassy carbon ring—disc electrode: Part 1. Method and instrumentation with evaluation of some parameters

The equipment and procedure are described for the determination without preconcentration of several heavy metals based on d.c. anodic stripping voltammetry at a rotating ring—disc glassy carbon electrode with in situ mercury plating. During stripping of the metals deposited on the disc, the current from the reduction of the ions collected at the ring is measured. Some parameters (scan rate, thickness of the mercury film, electrode rotation and deposition time) influencing the ring collection peak current are examined experimentally. The results are compared with the theoretical considerations given by de Vries and van Dalen for anodic stripping voltammetry on a stationary mercury film electrode and by Bakanov et al. for a rotating mercury film electrode.     

Anodic Stripping Voltammetry Combined with Sequential Injection Analysis for Measurements of Trace Metal Ions with Bismuth‐ and Antimony Film Electrodes under Comparable Conditions

Anodic stripping voltammetry combined with sequential injection analysis (ASV‐SIA) was selected to examine the use of bismuth‐ and antimony‐film plated glassy carbon electrodes under comparable conditions for the determination of Pb(II) and Cd(II) ions. Of interest were the conditions for film deposition, as well as the composition of sample/carrier solutions, including concentrations of Sb(III) or Bi(III) and HCl. Then, by the optimized procedure, one could determine Pb(II), Cd(II), and Zn(II) ions at the low µg L^?1 level and ASV‐SIA configuration with both electrodes tested on analysis of a water sample.     

Determination of mobile form contents of Zn, Cd, Pb and Cu in soil extracts by combined stripping voltammetry

The amount of mobile forms of Zn, Pb, Cd and Cu in extracts obtained by treating soil samples with ammonium nitrate were determined by an appropriate combination of anodic and cathodic stripping voltammetry with hanging mercury drop electrode. Every analysis required three mercury drops: on the first one, zinc was determined; on the second, cadmium and lead; on the third, copper was determined. Zinc, lead and cadmium were determined by conventional differential-pulse anodic stripping voltammetry. For copper determination, adsorptive differential-pulse cathodic stripping voltammetry with amalgamation using chloride ions as a complexing agent was applied. The standard deviation of the results was from 1 to 10% depending on the metal content in the sample. Voltammetric results were in good agreement with the AAS analysis. No microwave digestion of soil extracts was necessary.     

Exploiting flow injection and sequential injection anodic stripping voltammetric systems for simultaneous determination of some metals

Flow injection (FI) and sequential injection (SI) systems with anodic stripping voltammetric detection have been exploited for simultaneous determination of some metals. A pre-plated mercury film on a glassy carbon disc electrode was used as a working electrode in both systems. The same film can be repeatedly applied for at least 50 analysis cycles, thus reducing the mercury consumption and waste. A single line FI voltammetric system using an acetate buffer as a carrier and an electrolyte solution was employed. An injected standard/sample zone was mixed with the buffer in a mixing coil before entering a flow cell. Metal ions were deposited on the working electrode by applying a potential of −1.1 V vs Ag/AgCl reference electrode. The stripping was performed by anodically scanning potential of working electrode to +0.25 V, resulting a voltammogram. Effects of acetate buffer concentration, flow rate and sample volume were investigated. Under the selected condition, detection limits of 1 μg l⁻¹ for Cd(II), 18 μg l⁻¹ for Cu(II), 2 μg l⁻¹ for Pb(II) and 17 μg l⁻¹ for Zn(II) with precisions of 2–5% (n=11) were obtained. The SI voltammetric system was similar to the FI system and using an acetate buffer as a carrier solution. The SI system was operated by a PC via in-house written software and employing an autotitrator as a syringe pump. Standard/sample was aspirated and the zone was then sent to a flow cell for measurement. Detection limits for Cd(II), Cu(II), Pb(II) and Zn(II) were 6, 3, 10 and 470 μg l⁻¹, respectively. Applications to water samples were demonstrated. A homemade UV-digester was used for removing organic matters in the wastewater samples prior to analysis by the proposed voltammetric systems.     

Electrodeposition of mercury film on electrodes modified with clay minerals

A new type of carbon paste electrode modified with clay mineral and covered with a mercury film is presented in this work. Electrodeposition of the mercury film was performed on the carbon paste electrode modified with montmorillonite. The mercury film was deposited by both electrodeposition in situ and a preliminary electrodeposition. The pre-deposited film of mercury showed to be suitable for anodic stripping voltammetry. An open-circuit sorption of Cd, Pb, and Cu with subsequent anodic stripping voltammetry exhibited higher current responses of metals. Besides the enhanced sensitivity superior separation of the current responses during a simultaneous stripping of metals is expected to be achieved by means of the newly prepared electrode. Presented at the 57th Congress of Chemical Societies, Tatranské Matliare, 4–8 September 2005.     

Analytical possibilities of microelectrode use for stripping voltammetry

The analytical utility of microelectrodes for stripping voltammetry is discussed from several points of view. The application of microelectrodes for microanalysis is demonstrated using a novel capillary flow injection system. Heavy metals at g l^–1 concentrations have been determined in l-samples. The influence of electrode size and convection during the deposition period of anodic stripping voltammetry on the reproducibility of trace metal determination was studied for various types of electrodes. In the case of mercury film microelectrodes, the precision can be improved if the accumulation of the analyte is performed under quiescent conditions. Practical examples of stripping voltammetry with microelectrodes such as copper determination in whisky and trace metal measurements in drinking water are given.     

预镀铋膜阳极溶出伏安法测定废水中微量铅和镉

本文采用预镀铋膜法修饰玻碳电极,并用该电极对废水中微量铅和镉同时进行了阳极溶出伏安法测定,研究了预镀铋膜测定铅和镉的条件。实验结果表明:铅和镉在铋膜电极上可得到灵敏的电位溶出峰,峰高和溶出电位与汞膜电极法相近,使用预镀铋膜电极可避免使用汞电极带来的环境污染。     

Poly(ester sulphonic acid) coated mercury thin film electrodes: characterization and application in batch injection analysis stripping voltammetry of heavy metal ions

Mercury-thin film electrodes coated with a thin film of poly(ester sulphonic acid) (PESA) have been investigated for application in the analysis of trace heavy metals by square wave anodic stripping voltammetry using the batch injection analysis (BIA) technique. Different polymer dispersion concentrations in water/acetone mixed solvent are investigated and are characterised by electrochemical impedance measurements on glassy carbon and on mercury film electrodes. The influence of electrolyte anion, acetate or nitrate, on polymer film properties is demonstrated, acetate buffer being shown to be preferable for stripping voltammetry applications. Although stripping currents are between 30 and 70% less at the coated than at bare mercury thin film electrodes, the influence of model surfactants on stripping response is shown to be very small. The effect of the composition of the modifier film dispersion on calibration plots is shown; however, detection limits of around 5 nM are found for all modified electrodes tested. This coated electrode is an alternative to Nafion-coated mercury thin film electrodes for the analysis of trace metals in complex matrices, particularly useful when there is a high concentration of non-ionic detergents.     

Voltammétrie de l'argent par redissolution anodique sur electrode de carbone vitreux et application au dosage de l'argent dans l'uranium et le pluton

Anodic stripping voltammetry of silver on a glassy carbon electrode, and application to the determination of silver in uranium and plutonium.The use of a glassy carbon electrode for the anodic stripping voltammetry of silver, without deposition of a preliminary mercury film is described. The deposition time, scan rate, rotation speed and molarity of the sulfuric solution have been studied; the method is applied to the determination of silver in uranium and plutonium.     

Microfluidic sequential injection analysis system based on polydimethylsiloxane (PDMS) chip with integrated pneumatic-actuated valves

A sequential injection analysis (SIA) system based on polydimethylsiloxane (PDMS) chip with integrated pneumatic-actuated valves was developed. A novel SIA operation mode using multiphase laminar flow effect and pneumatic microvalve control was proposed. The sample and reagent solutions were synchronously loaded and injected in the chip-based sample injection module instead of multi-step sequential injection by a multiposition valve and a reciprocating pump as in conventional SIA system. The sample and reagent injection volumes were reduced to ca. 1.1 nL. The present system has the advantages of simple structure, fast and convenient operation, low sample and reagent consumption, and high degree of integration and automation. The system operation conditions were optimized using fluorescein as model sample. Its feasibility in biological analysis was preliminarily demonstrated in enzyme inhibition assay.     

The determination of copper,lead and cadmium in sea water by differential pulse anodic stripping voltammetry

The effect of various instrumental parameters is investigated and optimized conditions established. The results are in accordance with the theory of differential pulse anodic stripping voltammetry. Both a hanging mercury drop electrode, and a rotating glassy carbon electrode mercury plated in situ were used. The best detection limit is obtained with the mercury film electrode, but the hanging mercury drop electrode is more reproducible. The differential pulse stripping technique is compared to linear sweep stripping, and increased sensitivity and better peak separation is demonstrated for the former technique, particularly when a hanging mercury drop electrode is used. However, the differential pulse technique will also improve the detection limit for a mercury film electrode, if the electrode has a non-ideal response with a corresponding high background current.     

Determination of Barium by Stripping Voltammetry

The behavior of barium(II) at a mercury electrode in 0.1 M KCl and 0.1 to 0.001 M KI solutions was studied by stripping voltammetry. The conditions for barium(II) accumulation on a silver-supported mercury film electrode were selected. Procedures for determining barium in potassium salts by stripping voltammetry were proposed.     

Signal stability of Nafion-coated thin mercury film electrodes for stripping voltammetry

The signal stability of the Nafion-coated thin mercury film electrode (NCTMFE) was studied by using cadmium and lead as test analytes and differential pulse anodic stripping voltammetry as detection method. In particular, the effect of the casting solvent and the curing procedure employed in the preparation of the polymer film was examined. Best results were obtained with N,N-dimethylacetamide as casting solvent and a two-step curing procedure in which the polymer was evaporated to dryness at 55 degrees and cured at 105 degrees with a hot-air gun. Mercury plating was performed ex situ. An NCTMFE prepared in this manner has a better signal stability than ex situ-plated as well as in situ-plated conventional mercury film electrodes.     

Flow injection analysis with detection at mercury drop electrode in the presence of surfactants

The surfactant presence in a sample may cause distortion of the flow injection peak obtained with amperometric detection at a mercury drop electrode. Distortion depends on detection parameters and flow system operating parameters and in some cases it may be eliminated by their careful optimization. Introduction of fumed silica into the carrier solution allows the dynamic removal of surfactant during the sample passage through the mixing coil. In the case of higher surfactant concentration in the sample, addition of fumed silica directly to the sample may be effective. Examples with amperometric detection as well as anodic stripping and adsorptive stripping voltammetric detection are described.     

Effect of the modification of mercuric oxide on the properties of mercury films at HgO-modified carbon paste electrodes

The influence of modifications of the mercuric oxide on the voltammetric properties of mercury film carbon paste electrodes was studied. The mercury film was formed electrochemically from the bulk red or yellow mercuric oxide-modified carbon paste electrodes. Differential pulse anodic stripping voltammetry and optical microscopy in polarised light were used to characterise the properties of the mercury films. The results were compared with those obtained using the conventional preparation of mercury-plated carbon paste electrodes when the mercury film is deposited on the surface of the electrode by reduction of Hg(II) ions in solution utilising a sufficient negative potential. It was shown that the mercury film formed from the yellow modification of the mercuric oxide provides better voltammetric characteristics than the red one owing to the high distribution of its small particles, i.e. the mercury droplets after electrochemical treatment. Such a mercury film has similar properties to those of a mercury film generated from solution. Received: 06 December 1999 / Accepted: 16 March 2000     

The differential pulse anodic stripping voltammetry of copper and lead and their determination in EDTA extracts of soils with the mercury film glassy carbon electrode

The differential pulse anodic stripping voltammetry of copper and lead at the mercury film glassy carbon electrode is discussed. The mercury film prevents the occurrence of a monolayer stripping peak for copper. The influence of antimony and bismuth on the anodic stripping voltammetric behaviour of copper and lead is discussed. An interaction between copper and antimony distorts the copper stripping peak and gives rise to an intermediate peak. The method described is suitable for determining copper and lead simultaneously in EDTA extracts of soils.