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Electrochemical stripping techniques are recognized aspowerful tools for trace heavy metal detection due to theirunique ability to preconcentrate target metals during theaccumulation step, most commonly potentiostatically asamalgams on the mercury electrode [1]. In certain cases,where the analyte reacts irreversibly, forms intermetalliccompounds or cannot form an amalgam (e.g., Co, Ni),the adsorptive stripping protocol is proposed, whereby acomplexing reagent, usually dimethylglyoxime (DMG) isadded to the measuring solution, forming a complex withthe target metal, which is subsequently adsorbed onto theelectrode, commonly a mercury film or mercury drop[2–8]. There are also reports in which the electrode ismodified with a complexing reagent, e.g.,DMG,allowingthe target metal to be simultaneously complexed and accumulatedonto the electrode [9,10]. Following the accumulationstep, the adsorbed metal complex is stripped offthe electrode surface either voltammetrically or chronopotentiometrically.The most notable advantages of thechronopotentiometric mode are signal independence ofthe electrode surface, detection in the presence of someelectroactive organic compounds, lower backgroundcontributions, and analysis in solutions with lower ionicstrength [11–13].In the last five decades, despite its well-known toxicity,different mercury electrodes have been widely usedin stripping analysis. There were several reports suggestingthe replacement of mercury with some othermaterials, e.g., gold, platinum, iridium, different modificationsof carbon and others, but none of them approachedthe favorable electrochemical behavior ofmercury [14,15]. Recently, we demonstrated the veryattractive electrochemical characteristics of bismuth,which compare favorably with mercury analoguesregarding anodic stripping voltammetric and strippingchronopotentiometric determination of some traceheavy metals [16–21]. In addition, carbon paste electrodesmodified with bismuth film, in connection tostripping voltammetry, were also studied [22,23]. Wangand Lu [24] also report on adsorptive stripping voltammetricdetection of trace nickel.In the present article, we first report on the simultaneousdetection of trace cobalt and nickel using BiFE,which represents a promising replacement for toxicmercury electrodes. We employed adsorptive strippingconstant current chronopotentiometric and adsorptivestripping voltammetric protocol, with DMG acting ascomplexing reagent. A comparison with the mercurycounterpart is also given.
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