Bogusław Baś

Preparation of Silver Surface for Mercury Film Electrode of Prolonged Analytical Application

The surface of a silver wire of a fibrous texture, pretreated by storing in Hg(Ag) is converted into a fine crystalline solid amalgam in the form of a passive skin layer. Applied as the base surface for film electrode, but containing some amount of silver, this layer replaces very well the pure mercury as an electroactive liquid layer.The apparatus for cyclic renovation of the film thickness from 50 nm to 70 nm is described. The promising analytical parameters such as the reproducibility and low residual current are presented.

The cyclic renewable mercury film silver based electrode for determination of molybdenum(VI) traces using adsorptive stripping voltammetry.

The new cyclic renewable mercury film silver based electrode (Hg(Ag)FE), applied for the determination of molybdenum(VI) traces using differential pulse adsorptive cathodic stripping voltammetry (DP AdSV) is presented. The Hg(Ag)FE electrode is characterized by very good surface reproducibility (<or=2%) and long-term stability (more than 2 thousand measurement cycles). The preparation of the Hg(Ag)FE is very simple and its operation may be controlled automatically. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimized. The calibration graph is linear from 2 nM (192 ng L(-1)) to 200 nM (19 microg L(-1)) for an accumulation time of 15s, with correlation coefficient of 0.9995. For a Hg(Ag)FE with a surface area of 3.5mm(2) the detection limit for an accumulation time of 60s is as low as 8 ng L(-1). The repeatability of the method at a concentration level of the analyte as low as 2.4 microg L(-1), expressed as R.S.D. is 1.3% (n=7). The proposed method was successfully applied and validated by studying the certified reference material TMRAIN-95 and simultaneous recovering of Mo(VI) from spiked water and sediment samples.

Application of renewable silver amalgam annular band electrode to voltammetric determination of vitamins C, B1 and B2

In this work, the design and results of applying silver liquid amalgam film-modified silver solid amalgam annular band electrode (AgLAF-AgSAE), refreshed before each measurement, to voltammetric determination of vitamins C (VC), B(1) (VB1) and B(2) (VB2) are presented. The method is based on adsorptive accumulation of analytes at the AgLAF-AgSAE in a phosphate buffer (VB1), phosphate buffer with Triton X-100 (VB2) and an alkaline borate buffer with Triton X-100 (VC). The analytical parameters and procedure of electrode activation were optimized. The calibration graphs obtained for vitamins C, B(1) and B(2) are linear, respectively, for concentration range 0.05-12, 0.01-0.1 and 0.05-3 mg L(-1). The detection limits were calculated and equaled 0.02, 0.003 and 0.009 mg L(-1), while repeatability of the peak current was 2%, 1% and 3%, respectively. These results are comparable with results obtained for polarographic determination of the same vitamins using mercury electrodes. Finally, the AgLAF-AgSAE was applied to the determination of vitamins in pharmaceutical samples and fruit juices with satisfactory results.

The renovated silver ring electrode in determination of lead traces by differential pulse anodic stripping voltammetry.

The study of a new type of working electrode - the renovated silver ring electrode (RSRE) - for lead ions detection via differential pulse anodic stripping voltammetry (DP ASV) without removal of oxygen is reported. The only four constituents of the RSRE: a specially constructed silver ring electrode, a silver sheet used as silver counter/quasi-reference electrode and a silicon O-ring, are fastened together in a polypropylene body. The renovation of this electrode is carried out through mechanical removal of solid contaminants and electrochemical activation in the electrolyte which fills the RSRE body. Excellent repeatability and reproducibility - also in organic samples solutions - were reached in a period of a few weeks through the renovation of the electrode surface before each measurement. The reduction and stripping of lead on silver electrode under the DP ASV conditions are underpotential deposition/dissolution phenomena. The RSRE is used for the determination of Pb ions in concentrations ranging from 1 x 10(-9) to 1 x 10(-7)M. The repeatability of DP ASV runs in synthetic solutions covering the entire concentration range is better than 2%. Obtained calibration curves are represented by a correlation coefficient of at least 0.999. The detection limit (LOD) for the time of electrodeposition equal to 60s is 0.2 x 10(-9)M. LOD for Pb(2+) detection at the RSRE is similar to this reported for a rotating silver electrode in subtractive anodic stripping voltammetry (E. Kirowa-Eisner, et al., Anal. Chim. Acta, 385 (1999) 325). The analysis of Pb(2+) in synthetic solutions with and without surfactants, certified reference materials and natural water samples have been performed.

The renewable bismuth bulk annular band working electrode: Fabrication and application in the adsorptive stripping voltammetric determination of nickel(II) and cobalt(II)

The paper presents the first report on fabrication and application of a user friendly and mercury free electrochemical sensor, with the renewable bismuth bulk annular band working electrode (RBiABE), in stripping voltammetry (SV). The sensor body is partly filled with the internal electrolyte solution, in which the RBiABE is cleaned and activated before each measurement. Time of the RBiABE contact with the sample solution is precisely controlled. The usefulness of this sensor was tested by Ni(II) and Co(II) traces determination by means of differential pulse adsorptive stripping voltammetry (DP AdSV), after complexation with dimethylglyoxime (DMG) in ammonia buffer (pH 8.2). The experimental variables (composition of the supporting electrolyte, pre-concentration potential and time, potential of the RBiABE activation, and DP parameters), as well as possible interferences, were investigated. The linear calibration graphs for Ni(II) and Co(II), determined individually and together, in the range from 1×10(-8) to 70×10(-8)molL(-1) and from 1×10(-9) to 70×10(-9)molL(-1) respectively, were obtained. The calculated limit of detection (LOD), for 30s of the accumulation time, was 3×10(-9)molL(-1) for Ni(II) in case of a single elements analysis, whereas the LOD was 5×10(-9)molL(-1) for Ni(II) and 3×10(-10)molL(-1) for Co(II), when both metal ions were measured together. The repeatability of the Ni(II) and Co(II) adsorptive stripping voltammetric signals obtained at the RBiABE were equal to 5.4% and 2.5%, respectively (n=5). Finally, the proposed method was validated by determining Ni(II) and Co(II) in the certified reference waters (SPS-SW1 and SPS-SW2) with satisfactory results.

Determination of trace arsenic on hanging copper amalgam drop electrode

Hanging copper amalgam drop electrode has been applied for trace determination of arsenic by cathodic stripping analysis. Detection limit for As(III) as low as 0.33nM (0.02mug/L) at deposition time (240s) could be obtained. For seven successive determinations of As(III) at concentration of 5nM relative standard deviation was 2.5% (n=7). Interferences from selected metals and surfactant substances were examined. Absence of copper ions in sample solution causes easier optimization and makes method less vulnerable on contamination. The developed method was validated by analysis of certified reference materials (CRMs) and applied to arsenic determinations in natural water samples.

Application of bismuth bulk annular band electrode for determination of ultratrace concentrations of thallium(I) using stripping voltammetry.

A study of a new type of mercury-free working electrode - the bismuth bulk annular band working electrode (BiABE) - applied for thallium(I) detection via differential pulse anodic stripping voltammetry (DP ASV), preceded by the complexation of interfering ions (Cd(2+), Pb(2+)) with EDTA in an acetate buffer (pH 4.5), is reported. The optimisation of experimental conditions included selection of the appropriate supporting electrolyte solution, potential and time of preconcentration, and DP mode parameters. The peak current was proportional to the concentration of Tl(I) in the range from 0.5 to 49nmolL(-1) (R=0.9992) and from 0.05 to 1.4nmolL(-1) (R=0.9987) for accumulation times of 60s and 300s, respectively. For 60s of accumulation time, the LOD was 0.005nmolL(-1) (1ngL(-1)) (at S/N=3), and the sensitivity of 18.5nA/nM was achieved. The relative standard deviation for 4.9nmolL(-1) of Tl(I) was 4.3% (n=5). Finally, the proposed method was successfully applied to determine Tl(I) in the certified reference materials-waters (SPS-SW1 and SPS-SW2) as well as the spiked tap and river water samples.

Sensitive voltammetric determination of gallium in aluminium materials using renewable mercury film silver based electrode

Simple cyclic renewable silver amalgam film electrode (Hg(Ag)FE), applied for the determination of gallium(III) using differential pulse anodic stripping voltammetry (DP ASV), is presented. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimised. The calibration graph is linear from 5 nM (0.35 µg L−1) to 80 nM (5.6 µg L−1) for a preconcentration time of 60 s, with correlation coefficient of 0.995. For a Hg(Ag)FE with a surface area of 9.9 mm2 the detection limit for a preconcentration time of 120 s is as low as 0.1 µg L−1. The repeatability of the method at a concentration level of the analyte as low as 3.5 µg L−1, expressed as RSD is 3.2% (n = 5). The proposed method was successfully applied by studying the synthetic samples and simultaneously recovery of Ga(III) from spiked aluminium samples.

NEW MULTIPURPOSE ELECTROCHEMICAL ANALYZER FOR SCIENTIFIC AND ROUTINE TASKS

This work presents a modernized and improved analyzer, different versions of which have been developed by our team over the past 30 years. Modern solutions and fully integrated chips have been applied to this device, which is dedicated to measuring low and very low levels of a recorded value. The up-to-date software fulfills the requirements of scientists, routine analysts, teachers, and students in the areas of electrochemical measurements and the interpretation of recorded signals. The proposed multipurpose analyzer ensures full measuring capability and allows the control of different electrochemical sensors, including the controlled growth mercury drop electrode (CGMDE). Various typical and more advanced signal processing procedures are built-in and are easily accessible.

Early lifetime zinc supplementation protects zinc-deficient diet-induced alterations

Preclinical and clinical data indicate the involvement of zinc in the pathophysiology and therapy of depression. A relationship between zinc-deficiency and depression symptoms was recently proposed. The present study investigated alterations in spontaneous locomotor activity and zinc concentrations in the serum, hippocampus and frontal cortex; these alterations were induced by subjecting rats to a zinc-deficient diet, prior subjected after birth to zinc-supplemented diet. Body weight was significantly reduced in animals subjected to the four-week zinc-deficient diet compared to those subjected to the zinc-adequate diet. The two-week zinc-deficient diet induced a significant increase in locomotor activity in all measured time periods (5, 30 and 60 min by 44-62%). The four-week zinc-deficient diet did not affect locomotor activity, while the six-week zinc-deficient diet resulted in a 45% increase in the 5 min time period. Serum zinc concentrations were significantly reduced (by 29%) in animals subjected to the four-week zinc-deficient diet but not in those subjected to the two- or six-week zinc-deficient diets. The zinc-deficient diet did not influence the zinc concentration in the examined brain regions regardless of the length. These results indicate that post-birth supplementation with zinc may protect zinc-deficient diet-induced rapid alterations in zinc homeostasis.