The Use of a Solid Bismuth Microelectrode for Vanadium Quantification by Adsorptive Stripping Voltammetry in Environmental Water Samples

Abstract

This paper presents for the first time the use of an environmentally friendly solid bismuth microelectrode for the voltammetric quantification of V(V) in natural water samples. These studies were designed to replace the film bismuth electrode that had been introduced to eliminate the conventional sensors based on highly toxic mercury. In the proposed procedure, V(V) is preconcentrated at the solid bismuth microelectrode surface via the formation of electroactive complexes with cupferron from a solution of 0.1-mol L−1 acetate buffer, pH = 4.6 at a potential of −0.4 V. The linearity of the calibration graph is in the V(V) concentration range from 8 × 10−10 to 1 × 10−7 mol L−1 with a preconcentration time of 1 min. The limit of detection (calculated as 3 σ) is 2.5 × 10−10 mol L−1 for a preconcentration time of 1 min. It was also demonstrated that significant improvement in analytical parameters was achieved as a result of the activation of the solid electrode surface at a potential of −2.5 V for 2 s. The developed procedure is highly selective for the presence of foreign ions and organic compounds in tested samples. The accuracy of the recommended procedure was checked using SPS-WW1 waste water-certified reference materials of a complex composition, in which the concentration of V(V) determined by the proposed method was 95.1 ± 1.6 ng mL−1. Moreover, in keeping with the outlined procedure, river, tap and rain water samples were analyzed without any pretreatment, and recovery values from 96% to 106% were obtained.

Adsorptive Stripping Voltammetry for Determination of Vanadium: A Review

“…The complexing agents used in the voltammetric analysis of vanadium are listed in Table 1 , together with the detection limits obtained. The most commonly chosen complexing agent in voltammetric procedures for the determination of vanadium is cupferron [ 45 , 46 , 47 , 48 , 49 , 50 ]. Other complexing agents are also used, such as chloranilic acid [ 51 , 52 , 53 , 54 ], catechol [ 55 ], chromoxane cyanine R [ 56 ], alizarin violet [ 57 ], pyrocatechol [ 58 ], 2,3–dihydroxybenzaldehyde [ 59 ], galic acid [ 60 ], pyrogallol [ 61 ], quertic–5–sulfonic [ 62 ] and 2,3–dihydroxynaphthalene [ 63 ].…”

“…Much cheaper and simple methods are voltammetric techniques [ 39 , 40 , 41 , 42 , 43 , 44 ]. The method of choice is adsorptive stripping voltammetry (AdSV), which is also used to determine vanadium in natural samples [ 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 ]. The most important parameters and characteristics of these procedures are summarized and presented in Table 1 .…”

“…In the case of the use of stripping voltammetry in the determination of vanadium, AdSV is mainly used, whereby various complexing agents that form electrochemically active complexes with VO 2 (+) are used and undergo adsorption on various working electrodes. As can be seen in Table 1 , dozens of such procedures have been described in the literature, with vanadium detection limits ranging from 2.8 × 10 −12 to 1 × 10 −7 mol L −1 [ 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 ]. In the case of vanadium determination, anodic stripping voltammetry (ASV) is very rarely used, in which the determination is based on redox reactions associated with the change in the oxidation state of vanadium, and few papers on this are available in the literature [ 41 , 44 ].…”

Supporting Electrolyte Manipulation for Simple Improvement of the Sensitivity of Trace Vanadium(V) Determination at a Lead-Coated Glassy Carbon Electrode

“…Of these techniques, only the SV can be used in routine field vanadium analysis. Adsorptive stripping voltammetry (AdSV), based on the accumulation of vanadium complexes with various complexing agents (such as chloranilic acid [ 11 , 12 , 13 , 14 ], cupferron [ 15 , 16 ], gallic acid [ 17 ], alizarin red S [ 18 ], alizarin violet [ 19 ], 2,3-dihydrobenzaldehide [ 20 ], and quercetin-5-sufonic acid [ 21 ]) on the electrode surface, has proven to be especially useful for the trace determination of vanadium. As can be seen, the most commonly used complexing agents are chloranilic acid and cupferron.…”

“…Moreover, the toxicity of mercury limits the use of mercury electrodes in the analytical practice. Less toxic electrodes, such as bismuth-based electrodes, were applied to V(V) determination [ 12 , 16 , 17 ]. However, the detection limit of bismuth-based electrodes (2.5 × 10 −10 mol L −1 ) is higher than that of HMDE.…”