Trace analysis, stripping voltammetry

Stripping voltammetry or stripping analysis has a special place in electrochemistry because of its extensive application in trace metal analysis. Stripping voltammetry (SV) is a two-step process as shown schematically in Fig. 18b. 12. In the first step, the metal ion is reduced to metal on a mercury electrode (thin mercury film on glassy carbon or a HMDE) as amalgam. 

Differential pulse polarography and stripping voltammetry have been applied to the analysis of trace metals in airborne particulates, incinerator fly ash, rocks. 

Miscellaneous Samples Besides environmental and clinical samples, differential pulse polarography and stripping voltammetry have been used for the analysis of trace metals in other samples, including food, steels and other alloys, gasoline, gunpowder residues, and pharmaceuticals. Voltammetry is also an important tool for... 

Anodic stripping voltammetry at a mercury film electrode can be used to determine whether an individual has recently fired a gun by looking for traces of antimony in residue collected from the individual s hands, fn a typical analysis a sample is collected with a cotton-tipped swab that had been wetted with 5% v/v HNO3. When returned to the lab, the swab is placed in a vial containing 5.00 mb of 4 M HCl that is 0.02 M in hydrazine sulfate. After allowing the swab to soak overnight,... 

Pretreatment of the collected particulate matter may be required for chemical analysis. Pretreatment generally involves extraction of the particulate matter into a liquid. The solution may be further treated to transform the material into a form suitable for analysis. Trace metals may be determined by atomic absorption spectroscopy (AA), emission spectroscopy, polarogra-phy, and anodic stripping voltammetry. Analysis of anions is possible by colorimetric techniques and ion chromatography. Sulfate (S04 ), sulfite (SO-, ), nitrate (NO3 ), chloride Cl ), and fluoride (F ) may be determined by ion chromatography (15). 

Most of our understanding of the marine chemistry of trace metals rests on research done since 1970. Prior to this, the accuracy of concentration measurements was limited by lack of instrumental sensitivity and contamination problems. The latter is a consequence of the ubiquitous presence of metal in the hulls of research vessels, paint, hydrowires, sampling bottles, and laboratories. To surmount these problems, ultra-clean sampling and analysis techniques have been developed. New methods such as anodic stripping voltammetry are providing a means by which concentration measurements can be made directly in seawater and pore waters. Most other methods require the laborious isolation of the trace metals from the sample prior to analysis to eliminate interferences caused by the highly concentrated major ions. 

Cadmium in acidified aqueous solution may be analyzed at trace levels by various instrumental techniques such as flame and furnace atomic absorption, and ICP emission spectrophotometry. Cadmium in solid matrices is extracted into aqueous phase by digestion with nitric acid prior to analysis. A much lower detection level may be obtained by ICP-mass spectrometry. Other instrumental techniques to analyze this metal include neutron activation analysis and anodic stripping voltammetry. Cadmium also may be measured in aqueous matrices by colorimetry. Cadmium ions react with dithizone to form a pink-red color that can be extracted with chloroform. The absorbance of the solution is measured by a spectrophotometer and the concentration is determined from a standard calibration curve (APHA, AWWA and WEF. 1999. Standard Methods for the Examination of Water and Wastewater, 20th ed. Washington, DC American Public Health Association). The metal in the solid phase may be determined nondestructively by x-ray fluorescence or diffraction techniques. 

Measurement of trace metals, including nickel in seawater can be completed using an in-line system with stripping voltammetry or chronopotentiometry (van den Berg and Achterberg 1994). These methods provide rapid analysis (1-15 minutes) with little sample preparation. The detection limit of these methods for nickel was not stated. Recommended EPA methods for soil sediment, sludge, and solid waste are Methods 7520 (AAS) and 6010 (ICP-AES). Before the widespread use of AAS, colorimetric methods were employed, and a mrmber of colorimetric reagents have been used (Stoeppler 1980). 

The concentration levels of most trace metals and metalloids lie below 1000 pg P . Therefore, the classical methods of analysis do not have the required sensitivity. Among the instrumental techniques that have been extensively used for the analysis of biological materials include, atomic absorption spectrometry, plasma emission spectrometry, anodic stripping voltammetry and neutron activation analysis. 

The analytical use of GECE modified in situ by using bismuth solution for square wave anodic stripping voltammetry (SWASV) of heavy metals is also studied [36]. The use of this novel format is a simpler alternative to the use of mercury for analysis of trace levels of heavy metals. The applicability of these new surface-modified GECE to real samples (tap water and soil samples) is presented. 

The majority of the works with HgCFMEs focused on the anodic stripping of metals [127]. However, our works have been mainly focused on the determination of organic molecules that show the ability of adsorption on mercury [119-121], for example pteridines. Therefore, those molecules can be primarily preconcentrated on HgCFMEs and, subsequently, determined by cathodic stripping techniques. This procedure is described like adsorptive stripping voltammetry and it is a very interesting technique for trace and ultratrace analysis due to its... 

Polarographic AC and pulse polarographic techniques as well as stripping analysis are effective tools for the determination of trace levels of metal ions. Table 3.1 provides a comparison of the sensitivity and usefulness of the various methods.12,21 23 For metal ions, stripping voltammetry usually is the method... 

Twenty years ago the main applications of electrochemistry were trace-metal analysis (polarography and anodic stripping voltammetry) and selective-ion assay (pH, pNa, pK via potentiometry). A secondary focus was the use of voltammetry to characterize transition-metal coordination complexes (metal-ligand stoichiometry, stability constants, and oxidation-reduction thermodynamics). With the commercial development of (1) low-cost, reliable poten-tiostats (2) pure, inert glassy-carbon electrodes and (3) ultrapure, dry aptotic solvents, molecular characterization via electrochemical methodologies has become accessible to nonspecialists (analogous to carbon-13 NMR and GC/MS). 

Kefala, G. and Economou, A. (2006), Polymer-coated bismuth film electrodes for the determination of trace metals by sequential-injection analysis/anodic stripping voltammetry. Anal. Chim. Acta, 576(2) 283-289. 

Abrasive stripping voltammetry — Technique where traces of solid particles are abrasively transferred onto the surface of an -> electrode, followed by an electrochemical dissolution (anodic or cathodic dissolution) that is recorded as a current-voltage curve [i]. It allows qualitative and quantitative analysis of metals, alloys, minerals, etc. The technique is a variant of - voltammetry of immobilized particles [ii]. 

Mader, P., Szakova, J., Curdova, E. Combination of classical dry ashing with stripping voltammetry in trace element analysis of biological materials review of literature published after 1978. Talanta 43, 521-534 (1996)... 

Zimmermann, S., Menzel, C.M., Berner, Z., Eckhardt, J.D., Stiiben, D., Alt, F., Messerschmidt, J., Taraschewski, H., Sures, B. Trace analysis of platinum in biological samples a comparison between sector field ICP-MS and adsorptive cathodic stripping voltammetry following different digestion procedures. Anal. Chim. Acta 439, 203-209 (2001)... 

Brezonik, P.L., Brauner, P.A., and Stumm, W. Trace metal analysis by anodic stripping voltammetry effect of sorption by natural and model organic compounds. Water Res. 10, 605-612 (1976). 

Anodic stripping voltammetry (ASV) was applied to the determination of copper traces present as Cu(dik)2. The differential pulse technique was used to strip the amalgamated copper from a hanging mercury drop electrode. The experimental variables such as scan rate of electrode potential, deposition potential, deposition time and stirring speed of the solution could be optimized. The linear range of the calibration plot was 0.05-1 (xM and the LOD was 0.014 fiM Cu(II). A method was used for the determination of copper in breast milk and beer as typical examples of application, consisting of minerahzation of the sample, extraction of Cu(II) from the aqueous solution with a 1 M solution of acacH in chloroform and ASV end analysis . 

Improvements on a computer-controlled instrument for performing trace-metal analysis by anodic stripping voltammetry are presented and discussed. The ease of operation of the instrument has been improved by the use of carbon-disc electrodes and spool-type Teflon valves. The device has been used to measure Zn, Cd, Pb, and Cu in estuarine waters recently an attempt was made to measure Cu in surface oceanic waters. Although the sensitivity and accuracy of the instrument appear insufficient for the measurement of Cu in oceanic surface waters, the approach appears promising for future work. 

Analytical methods have been developed which are sensitive enough to measure the low concentration levels of trace metals in seawater. Well defined methods, like emission spectroscopy, neutron activation analysis, anodic stripping voltammetry, atomic absorption spectroscopy, and mass spectroscopy, can be used individually or collectively to obtain the necessary data on trace metal concentrations. So why, even with these well developed methods, are we not getting reliable results from the analysis of trace metals in natural water ... 

Analytical techniques used for clinical trace metal analysis include photometry, atomic absorption spectrophotometry (AAS), inductively coupled plasma optical emission (ICP-OES), and inductively coupled plasma mass spectrometry (ICP-MS). Other techniques, such as neutron activation analysis (NAA) and x-ray fluorescence (XRF), and electrochemical methods, such as anodic stripping voltammetry (ASV), are used less commonly For example. NAA requires a nuclear irradiation facility and is not readily available and ASV requires completely mineralized solutions for analysis, which is a time-consuming process. 

R. Kalvoda, Adsorptive Stripping Voltammetry in Trace Aanalysis, (REVIEW), Contemp. Electroanal. Chem., [Proc.Electro-Finn Analysis, Int. Conf. Electroanal. Chem.] (1988) (Pub. 1990), Plenum Press, New York, pp 403-5. 

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