Anodic stripping voltammetry, lead

From the nature of the process described above it has been referred to as stripping polarography , but the term anodic stripping voltammetry is preferred. It is also possible to reverse the polarity of the two electrodes of the cell, thus leading to the technique of cathodic stripping voltammetry. 

Anodic stripping voltammetry (ASV) has been used extensively for the determination of heavy metals in samples of biological origin, such as lead in blood. ASV has the lowest detection limit of the commonly used electroanalytical techniques. Analyte concentrations as low as 10 M have been determined. Figure 16 illustrates ASV for the determination of Pb at a mercury electrode. The technique consists of two steps. The potential of the electrode is first held at a negative value for several minutes to concentrate some of the Pb " from the solution into the mercury electrode as Pb. The electrode process is... 

Morrell G, Giridhar G. 1976. Rapid micromethod for blood lead analysis by anodic stripping voltammetry. Clin Chem 22 221-223. 

Satzger RD, Clow CS, Bonnin E, et al. 1982. Determination of background levels of lead and cadmium in raw agricultural crops by using differential pulse anodic stripping voltammetry. J Assoc Off Anal Chem 65 987-991. 

Scarponi et al. [93] used anodic stripping voltammetry to investigate the contamination of seawater by cadmium, lead, and copper during filtration and storage of samples collected near an industrial area. Filtration was carried... 

Halliday et al. [396] have described a simple rapid graphite furnace method for the determination of lead in amounts down to 1 xg/l in polluted seawater. The filtered seawater is diluted with an equal volume of deionised water, ammonium nitrate added as a matrix modifier, and aliquots of the solution injected into a tantalum-coated graphite tube in an HGA-2200 furnace atomiser. The method eliminates the interference normally attributable to the ions commonly present in seawater. The results obtained on samples from the Firth of Forth (Scotland, UK) were in good agreement with values determined by anodic stripping voltammetry. 

Early work [400] on the application of cyclic and anodic stripping voltammetry to the determination of lead showed a poor correlation between peak current values and Pb11 concentration at high pH values. This is due to the low electrochemical activity of PbOH. 

Quentel et al. [402] studied the influence of dissolved organic matter in the determination of lead in seawater by anodic stripping voltammetry. 

Muzzarelli and Sipos [622] showed that a column of chitosan (15 x 10 mm) can be used to concentrate zinc from 3 litres of seawater before determination by anodic-stripping voltammetry with a composite mercury-graphite electrode. Zinc (and lead) are eluted from the column by 2 M ammonium acetate (50 ml), copper by 0.01 M EDTA (10 ml), and cadmium by 0.1 M potassium cyanide (3 ml). 

Brugmann et al. [680] compared three methods for the determination of copper, cadmium, lead, nickel, and zinc in North Sea and northeast Atlantic waters. Two methods consisted of atomic absorption spectroscopy but with preconcentration using either freon or methyl isobutyl ketone, and anodic stripping voltammetry was used for cadmium, copper, and lead only. Inexplicable discrepancies were found in almost all cases. The exceptions were the cadmium results by the two atomic absorption spectrometric methods, and the lead results from the freon with atomic absorption spectrometry and anodic scanning voltammetric methods. 

Scarponi et al. [781] studied the influence of an unwashed membrane filter (Millpore type HA, 47 mm diameter) on the cadmium, lead, and copper concentrations of filtered seawater. Direct simultaneous determination of the metals was achieved at natural pH by linear-sweep anodic stripping voltammetry at a mercury film electrode. These workers recommended that at least 1 litre of seawater be passed through uncleaned filters before aliquots for analysis are taken the same filter can be reused several times, and only the first 50-100 ml of filtrate need be discarded. Samples could be stored in polyethylene containers at 4 °C for three months without contamination, but losses of lead and copper occurred after five months of storage. 

Nygaard et al. [752] compared two methods for the determination of cadmium, lead, and copper in seawater. One method employs anodic stripping voltammetry at controlled pH (8.1,5.3 and 2.0) the other involves sample pretreatment with Chelex 100 resin before ASV analysis. Differences in the results are discussed in terms of the definition of available metal and differences in the analytical methods. 

Cuculic and Branica [788] applied differential pulse anodic stripping voltammetry to a study of the adsorption of cadmium, copper, and lead in seawater onto electrochemical glass vessels, quartz cells, and Nalgene sample bottles. Nalgene was best for sample storage and quartz was best for electroanalytical vessels. 

Batley [28] examined the techniques available for the in situ electrodeposition of lead and cadmium in estuary water. These included anodic stripping voltammetry at a glass carbon thin film electrode and the hanging drop mercury electrode in the presence of oxygen and in situ electrodeposition on mercury coated graphite tubes. Batley [28] found that in situ deposition of lead and cadmium on a mercury coated tube was the more versatile technique. The mercury film, deposited in the laboratory, is stable on the dried tubes which are used later for field electrodeposition. The deposited metals were then determined by electrothermal atomic absorption spectrometry, Hasle and Abdullah [29] used differential pulse anodic stripping voltammetry in speciation studies on dissolved copper, lead, and cadmium in coastal sea water. 

The principles of thin-layer anodic stripping voltammetry were discussed, and a model for the stripping stage was developed for anodization by a linear potential ramp [35]. The experimental test of the theories was carried out for cadmium and lead amalgams. 

Shams E, Abdollahi H, Yekehtaz M, Hajian R (2004) H-point standard additions method in the analysis by differential pulse anodic stripping voltammetry Simultaneous determination of lead and thin.Talanta 63 359-364. 

C. Because they were used in gasoline to boost octane rating, alkyl lead compounds found their way into the environment as toxic pollutants. One way to measure lead compounds in natural waters is by anodic stripping voltammetry (Figure 17-20), in which the lead is first reduced to the element at a mercury electrode and dissolves in the mercury. Reoxidation occurs when the electrode potential is made sufficiently positive, with current proportional to the concentration of dissolved Pb. 

The determination of lead in soil is also discussed under Multi-Cation Analysis in Sects. 2.55 (inductively coupled plasma atomic emission spectrometry), 2.55 (atomic absorption spectrometry), 2.55 (photon activation analysis), 2.55 (emission spectrometry), 2.55 (anodic stripping voltammetry) and 2.55 (neutron activation analysis). 

Opydo [224] used anodic stripping voltammetry to determine thallium in soil extracts in the presence of a large excess of lead. 

Lam, M.T., Chakrabarti, C.L., Cheng, J. and Pavski, V. (1997) Rotating disk electrode voltammetry/anodic stripping voltammetry for chemical speciation of lead and cadmium in freshwaters containing dissolved organic matter. Electroanalysis, 9, 1018-1029. 

Martinotti, W., Queirazza, G., Guarinoni, A. and Mori, G. (1995) In-flow speciation of copper, zinc, lead and cadmium in fresh waters by square wave anodic stripping voltammetry Part II. Optimization of measurement step. Anal. Chim. Acta, 305, 183-191. 

The four variations of this technique are to be found in Table 14.2. The schemes of operation are shown in Fig. 14.6. Important applications for trace metals are the use of anodic stripping voltammetry (ASV) to determine trace quantities of copper, cadmium, lead and zinc, and adsorptive stripping voltammetry (AdSV) of trace quantities of nickel and cobalt—pre-concentration by adsorption accumulation of the oxime complexes followed by reduction to the metal is employed, as reoxidation of these metals in ASV is kinetically slow and does not lead to well-defined stripping peaks. 

De-proteinisation of diluted whole blood, and acid extraction of lead from proteins with 2M HNOs is the preparation chosen for the National Bureau of Standards reference method for blood-lead analysis [28]. Centrifugation of blood samples treated in this way yields clear supernatant fractions that contain all of the lead present, and which are easily dispensed into electrothermal atomisers using auto-sampling techniques. This method gave results that compared very well with those obtained using anodic stripping voltammetry, r = 0.975, for concentrations of 10—900 pg l-1 of lead in blood [15]. 

Flow-injection analysis is also well-suited for the automation of anodic stripping voltammetry. Metals can be plated from the sample solution as it passes over the electrode. Stripping is then carried out in the deox-ygenated carrier stream (15, 34). The sample itself does not have to be deox-ygenated. Detection limits of 3 nM have been reported for lead by this technique (34). 

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