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Adsorptive stripping voltammetry (AdSV) has been establishedas a reliable trace metal analysis technique applicableto different samples [1]. Traditionally the hanging mercurydrop electrode (HMDE) has been used as the working electrodein AdSV but this electrode, despite its sensitivity, hasmany drawbacks that make it unsuitable for many applications[2]. Mercury film electrodes (MFE’s), prepared byelectroplating a thin film of mercury on a suitable substrate,have in many cases replaced the HMDE in AdSV withsatisfactory results [2]. The advantages of MFE’s over theHMDE are the precise mass-transfer of the analyte speciesto the electrode surface, their simplicity in terms of constructionand maintenance, their mechanical stability andthe scope for different cell configurations [3]. In particular,it has been possible to determine Ni(II) and Co(II) by AdSVafter complexation with different dioximes by employingMFE’s in different batch and flow–cell configurations [4–8].However, the increased risks associated with the use,manipulation and disposal of metallic mercury or mercurysalts have led some countries to completely ban mercury[9], and, as a result, new electrode materials with propertiescomparable to those of mercury are sought. Recently,bismuth-film electrodes BFE’s, consisting of a thin bismuthfilm deposited on a suitable substrate, have been shown tooffer comparable performance to MFE’s in anodic strippingvoltammetry (ASV) [10–13]. It has been shown that BFE’s
maintain all the advantages of MFE’s and, at the same time,
are environmetally-friendly as the toxicity of bismuth and
its salts is negligible. So far, the area of AdSV on BFE’s
remains largely unexplored, since neither does a systematic
study exist on the different parameters that affect the
determination of metals (including Ni(II) and Co(II)) on
BFE’s by AdSV, neither have applications to real samples
been reported. Three short communications that have published,
investigating the feasibility of utilising BFE’s in the
determination of Ni(II) or Co(II) by adsorptive stripping
analysis, only reported preliminary results [14–16].
In this work, the suitability of a rotating-disc BFE for
square-wave AdSV (SWAdSV) has been investigated for
the simultaneous trace determination of Ni(II) and Co(II)
after complexation with dimethylglyoxime (DMG). All the
relevant experimental parameters associated with the analysis
were systematically investigated for the first time with
the view to analyse samples with different Ni(II)–Co(II)
concentration ratios. The utility of the method developed
was demonstrated for the simultaneous determination of
Ni(II) and Co(II) by SWAdSV on BFE’s in different real
samples for the fist time.
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