Quantitative determination of zinc in milkvetch by anodic stripping voltammetry with bismuth film electrodes

Bismuth film electrode (BiFE) was shown to be an attractive alternative to common mercury film electrode (MFE) for anodic stripping voltammetric measurements. In this study, bismuth film, that was in situ deposited onto glassy carbon electrode, was used to detect zinc content of milkvetch, used in traditional Chinese medicine. Variables affecting the response have been evaluated and optimized. Experimental results showed a high response, with a good linearity (between 0.5 × 10⁻⁶ mol L⁻¹ and 3 × 10⁻⁶ mol L⁻¹) a good precision (R.S.D. = 3.58%) and a low detection limit (9.6 × 10⁻⁹ mol L⁻¹ with a 120 s anodic). The anodic stripping performance makes the bismuth film electrode very desirable for measurements of trace nutritive element zinc in milkvetch and should impart possible restrictions on the use of mercury electrode.     

Individual and simultaneous determination of lead, cadmium, and zinc by anodic stripping voltammetry at a bismuth bulk electrode

A bismuth bulk electrode (BiBE) has been investigated as an alternative electrode for the anodic stripping voltammetric (ASV) analysis of Pb(II), Cd(II), and Zn(II). The BiBE, which is fabricated in-house, shows results comparable to those of similar analyses at other Bi-based electrodes. Metal accumulation is achieved by holding the electrode potential at −1.4 V (vs. Ag/AgCl) for 180 s followed by a square wave voltammetric stripping scan from −1.4 to −0.35 V. Calibration plots are obtained for all three metals, individually and simultaneously, in the10-100 μg L⁻¹ range, with a detection limit of 93, 54, and 396 ng L⁻¹ for Pb(II), Cd(II), Zn(II), respectively. A slight reduction in slope is observed for Cd(II) and Pb(II) when the three metals are calibrated simultaneously vs. individually. Comparing the sensitivities of the metals when calibrated individually vs. in a mixture reveals that Zn(II) is not affected by stripping in a mixture. However, Pb(II) and Cd(II) have decreasing sensitivities in a mixture. The optimized method has been successfully used to test contaminated river water by standard addition. The results demonstrate the ability of the BiBE as an alternative electrode material in heavy metal analysis.     

Determination of cadmium, lead, copper and zinc in the acetic acid extract of glazed ceramic surfaces by anodic stripping voltammetric method

An anodic stripping voltammetric method has been developed for determination of cadmium, lead, copper and zinc in acetic acid extract of glazed ceramic surfaces. An aliquot of 4% (v/v) acetic acid solution was kept in a ceramic ware for 24 h in the dark, then 10 mL of the extracted solution was placed in a voltammetric cell. The solution was purged with oxygen free nitrogen gas for 3 min before deposition of the metals was carried out by applying a constant potential of −1.20 V versus Ag/AgCl to the hanging mercury drop electrode (HMDE) for 45 s. A square wave waveform was scanned from −1.20 to 0.15 V and a voltammogram was recorded. A standard addition procedure was used for quantification. Detection limits of 0.25, 0.07, 2.7 and 0.5 μg L⁻¹ for cadmium, lead copper and zinc, respectively, were obtained. Relative standard deviations for 11 replicate determinations of 100 μg L⁻¹ each of all the metals were in the range of 2.8-3.6%. Percentage recoveries obtained by spiking 50 μg L⁻¹ of each metal to the sample solution were in the range of 105-113%. The method was successfully applied to ceramic wares producing in Lampang province of Thailand. It was found that the contents of cadmium, lead, copper and zinc released from the samples were in the range of <0.01-0.16, 0.02-0.45, <0.14 and 0.28-10.36 μg dm⁻², respectively, which are lower than the regulated values of the Thai industrial standard. The proposed method is simpler, more convenient and more sensitive than the standard method based on FAAS.     

Anodic stripping voltammetry at in situ bismuth-plated carbon and gold microdisc electrodes in variable electrolyte content unstirred solutions

Carbon and gold microdisc electrodes (30 and 10 μm, respectively) have been tested as substrates for in situ bismuth film plating from unstirred solutions of variable acetate buffer content and were subsequently used in the anodic stripping voltammetry determination of Pb(II) and Cd(II) ions. The effects of Bi(III) concentration, analyte accumulation time, stirring as well as supporting electrolyte content have been studied. Under optimal conditions good voltammetric responses were obtained by means of square wave anodic stripping voltammetry in unstirred analyte solutions of 5 × 10⁻⁸ to 10⁻⁶ M, even in the absence of added buffer. In an indicative application, Pb(II) ion levels were determined in tap water using bismuth-plated carbon microdisc electrodes.     

Manganese detection in marine sediments: anodic vs. cathodic stripping voltammetry

Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60 s accumulation period of 7.4 × 10⁻⁷ M and a sensitivity of 0.24 A M⁻¹. The method was used to evaluate the manganese content of marine sediments taken from Šibenik, Croatia.     

Determination of cadmium with a sequential injection lab-on-valve by anodic stripping voltammetry using a nafion coated bismuth film electrode

This work exploited a sequential injection lab-on-valve (LOV) system for the determination of cadmium by anodic stripping voltammetry (ASV). A miniaturized electrochemical flow cell (EFC) was fabricated in LOV, in which a nafion coated bismuth film electrode was used as working electrode. The cadmium was electrodeposited on the electrode surface in bismuth solution, and measured with the subsequential stripping scan. Under optimal conditions, the proposed system responded linearly to cadmium concentrations in a range 2.0-100.0 μg L⁻¹. The detection limit of this method was found to be 0.88 μg L⁻¹. By loading a sample volume of 800 μL, a sampling frequency of 22 determinations h⁻¹ was achieved. The repeatability expressed as relative standard derivation (R.S.D.) was 3.65% for 20 μg L⁻¹ cadmium (n = 11). The established method was applied to analysis of trace cadmium in environmental water samples and the spiked recoveries were satisfactory.     

Application of thin-shielded mercury microelectrodes in anodic stripping voltammetry

The performance in anodic stripping voltammetry (ASV) of hemispherical mercury microelectrodes, fabricated by electrodeposition of liquid mercury on the surface of Pt microdisks which were surrounded by a rather thick or thin insulating shield, was compared. The Pt microdisks were produced by sealing a wire of 25 μm diameter into a glass capillary, and by coating the cylindrical length of the Pt wire with a cathodic electrophoretic paint. The ratio of the overall tip radius b, to the basal radius of the electrode a, so-called RG = b/a, was equal to 110 ± 10 and 1.52 ± 0.01 for the thick- and thin-shielded microdisk, respectively. The mercury microelectrodes were characterized by cyclic voltammetry at 1 mV s⁻¹, in 1 mM Ru(NH₃)₆³⁺ aqueous solution. The steady-state voltammogram recorded with the thin-shielded mercury microelectrode displayed less hysteresis, while the steady-state current was about 30% higher than that of the thicker one. This was a consequence of the additional flux due to diffusion from behind the plane of the electrode. The flux enhancement, which was operative at the thin-shielded mercury microelectrode during the deposition step in the ASV experiments, allowed recording stripping peaks for Cd and Pb, which resulted about 32% larger than those recorded at the thicker shielded mercury microelectrode, under same experimental conditions.The usefulness of the thin-shielded mercury microelectrode for ASV measurements in real samples was verified by determining the content of heavy metal ions released in the pore water (pH 4.5) of a soil slurry.     

Determination of Hg on poly(vinylferrocenium) (PVF)-modified platinum electrode

A new surface based on poly(vinylferrocenium) (PVF⁺)-modified platinum electrode was developed for determination of Hg²⁺ ions in aqueous solutions. The polymer was electrodeposited on platinum electrode by constant potential electrolysis as PVF⁺ClO₄⁻. Cl⁻ ions were then attached to the polymer matrix by anion exchange and the modified electrode was dipped into Hg²⁺ solution. Hg²⁺ was preconcentrated at the polymer matrix by adsorption and also complexation reaction with Cl⁻. Detection of Hg²⁺ was carried out by differential pulse anodic stripping voltammetry (DPASV) after reduction of Hg²⁺. Mercury ions as low as 5 × 10⁻¹⁰ M could be detected with the prepared electrode and the relative standard deviation was calculated as 6.35% at 1 × 10⁻⁶ M concentration (n = 6). Interferences of Ag⁺, Pb²⁺ and Fe³⁺ ions were also studied at two different concentration ratios with respect to Hg²⁺. The developed electrode was applied to the determination of Hg²⁺ in water samples.     

Sensitive and stable monitoring of lead and cadmium in seawater using screen-printed electrode and electrochemical stripping analysis

Sensitive and stable monitoring of heavy metals in seawater using screen-printed electrodes (SPE) is presented. The analytical performance of SPE coupled with square wave anodic stripping voltammetry (SWASV) for the simultaneous determination of Pb and Cd in seawater samples, in the low μg L⁻¹ range, is evaluated. The stripping response for the heavy metals following 2 min deposition was linear over the concentration range examined (10-2000 μg L⁻¹) with detection limits of 1.8 and 2.9 μg L⁻¹ for Pb and Cd, respectively. The accuracy of the method was validated by analyzing metal contents in different spiked seawater samples and comparing these results to those obtained with the well-established anodic stripping voltammetry using the hanging mercury drop electrode. Moreover, a certified reference material was also used and the results obtained were satisfactory.     

Utilising gallium for enhanced electrochemical copper analysis at the bismuth film electrode

A sensitive anodic stripping voltammetric procedure at the bismuth film electrode (BFE) for trace analysis of copper (II) in the presence of gallium is presented. The new protocol circumvents the problems of overlapping stripping signals between copper and bismuth that previously hampered the analysis of copper at the BFE. The results illustrate that the addition of gallium not only improves the reproducibility of the bismuth stripping signal but also facilitates much improved resolution between the stripping signals of bismuth and copper. Investigations into the effect of gallium on the stripping response of copper and bismuth were studied showing a 4:1 gallium:copper mole ratio produces optimum signals from bismuth and copper indicating a possible stoichiometric relationship. Optimisation of other key variables including electrolyte composition, accumulation parameters and appropriate waveform settings were studied and optimised. The optimised procedures show a range of linear calibration plots (R² > 0.994) ranging from 2 to 500 μg L⁻¹ and the relative standard deviation for a solution containing 100 μg L⁻¹ copper was 3.7% (n = 10). Utilising an accumulation time of 300 s the limit of detection was 1.4 μg L⁻¹ (S/N = 3). This technique was successfully applied to the analysis of copper in tap water representing the first successful copper determination in real samples using the BFE.     

Nafion/2,2'-bipyridyl-modified bismuth film electrode for anodic stripping voltammetry

This paper describes the fabrication, characterisation and the application of a Nafion/2,2′-bipyridyl/bismuth composite film-coated glassy carbon electrode (NC(Bpy)BiFE) for the anodic stripping voltammetric determination of trace metal ions (Zn²⁺, Cd²⁺ and Pb²⁺). The NC(Bpy)BiFE electrode is prepared by first applying a 2.5 mm³ drop of a coating solution containing 0.5 wt% Nafion and 0.1% (w/v) 2,2′-bipyridil (Bpy) onto the surface of a glassy carbon electrode, while the Bi film was plated in situ simultaneously with the target metal ions at −1.4 V. The main advantage of the polymer coated bismuth film electrode is that the sensitivity of the stripping responses is increased considerably due to the incorporation of the neutral chelating agent of 2,2′-bipyridyl (Bpy) in the Nafion film, while the Nafion coating improved the mechanical stability of the bismuth film and its resistance to the interference of surfactants. The key experimental parameters relevant to both the electrode fabrication and the voltammetric measurement were optimized on the basis of the stripping signals. With a 2 min deposition time in the presence of oxygen, linear calibration curves were obtained in a wide concentration range (about 2-0.001 μM) with detection limits of 8.6 nM (0.56 μg dm⁻³) for Zn²⁺, 1.1 nM (0.12 μg dm⁻³) for Cd²⁺ and 0.37 nM (0.077 μg dm⁻³) for Pb²⁺. For nine successive preconcentration/determination/electrode renewal experiments the standard deviations were between 3 and 5% at 1.2 μM for zinc and 0.3-0.3 μM concentration level for lead and cadmium, respectively, and the method exhibited excellent selectivity in the presence of the excess of several potential interfering metal ions. The analytical utility of the stripping voltammetric method elaborated was tested in the assay of heavy metals in some real samples and the method was validated by ICP-MS technique.     

Column preconcentration of mercury as HgI4 using methyltrioctylammonium chloride-naphthalene adsorbent with subsequent anodic stripping-differential pulse voltammetric determination

A sensitive and selective preconcentration method has been developed for mercury using naphthalene-methyltrioctylammonium chloride (Aliquat 336s) as an adsorbent. Mercury as HgI₄²⁻ was retained by the adsorbent in the column at a flow rate of 1 ml min⁻¹. The column was washed by a solution of sodium tetraphenylborate and sodium iodide to elute the adsorbed mercury. The eluents were collected in a 10 ml volumetric flask and diluted to the mark with water, transferred to a voltammetric cell and anodic stripping-differential pulse voltammetry was performed. Preconcentration factors of 40 and 80 could be achieved when using a 10 and 5 ml voltammetric cell, respectively. The calibration graph was linear in the range of 1.2-8.7 ng ml⁻¹ Hg(II) in the initial solution with r=0.9998 (n=6) and the 3 s detection limit was 0.13 ng ml⁻¹ when using a 10 ml cell. The relative standard deviation for eight replicate measurements of 1.2, 5.0 and 8.7 ng ml⁻¹ of Hg(II) in the initial solution was 0.51, 0.71 and 0.80%, respectively. The proposed method was successfully applied to determination of mercury in natural waters, wastewater and synthetic samples.     

Anodic stripping voltammetry at a new type of disposable bismuth-plated carbon paste mini-electrodes

A new type of disposable carbon paste mini-electrodes (CPmEs), with dimensions in the 50-300 μm range, have been fabricated by heat-shrinking the end-tip of plastic micropipette tips and filling them with carbon paste. The CPmEs have been characterized by microscopic and electrochemical means and tested as substrates for in situ plated Bi film electrodes (BiF-CPmEs), used in the determination of heavy metals by square wave anodic stripping voltammetry (SWASV). It was found that this new class of CPmEs combines the advantages of carbon paste electrodes (readily renewable surface and high surface area) with those of near-microelectrode behaviour (no stirring or electrolyte excess needed). During SWASV experiments in unstirred Pb(II) and Cd(II) solutions well-shaped stripping peaks were obtained whose height varied linearly with analyte concentration in the wide 1 × 10⁻⁸ to 10⁻⁶ M range, both in acetate buffer and unbuffered solutions. Under optimal conditions detection limits of 8 × 10⁻¹⁰ and 1.3 × 10⁻⁹ M were achieved for Pb(II) and Cd(II), respectively and in a trial application, these metal ions have been determined in a spiked tap water sample using a BiF-CPmE.     

Determination of Se(IV) by anodic stripping voltammetry using gold electrodes made from recordable CDs

This work presents a simple, reproducible and low cost method, employing differential pulse anodic stripping voltammetry, for determination of selenium(IV). A gold electrode obtained from recordable compact disks (CD-R) was used to evaluate the voltammetric behavior of the metallic ion in 0.1 mol L⁻¹ HClO₄. To evaluate the voltammetric behavior of Se(IV), parameters such as deposition potential and deposition time were optimized. A wide linear response range, from 0.5 to 291 ng mL⁻¹, was obtained using a 5.0 mm diameter gold electrode. Recovery tests for Se(IV) utilizing standard reference solutions provided values between 94 and 96%.     

Catalytic-adsorptive stripping voltammetric determination of ultra-trace iridium(III). Application to fresh- and sea-water

An extremely sensitive stripping voltammetric procedure for ultra-trace determination of iridium(III) is reported. The method is based on the interfacial accumulation of the iridium(III)-CTAB complex onto the glassy carbon electrode, followed by the catalytic reduction of the adsorbed complex in the presence of bromate. 0.3 mol L⁻¹ acetate buffer pH 4.7 + 6.9 × 10⁻² mol L⁻¹ NaBrO₃ + 2.7 × 10⁻⁵ mol L⁻¹ cetyltrimethylammonium bromide (CTAB) + 0.2 mol L⁻¹ KCl was employed as the supporting electrolyte.The analytical procedure was verified by the analysis of the standard reference materials: Sea Water BCR-CRM 403 and Fresh Water NIST-SRM 1643d.The accuracy, expressed as relative error e%, was satisfactory, being lower than 6%, while precision as repeatability, expressed as relative standard deviation s_r%, was generally lower than 5%. The limit of detection was of the order of 2-3 ng L⁻¹.Once set up on the standard reference materials, the analytical procedure was transferred and applied to superficial water sampled in proximity to superhighway and in the Po river mouth area.     

Characteristics of subtractive anodic stripping voltammetry of Pb and Cd at silver and gold electrodes

Silver and gold electrodes are useful for the quantitative determination of lead and cadmium with subtractive anodic stripping voltammetry (SASV). The use of SASV is essential for achieving good separation between the two peaks, to eliminate the interference of nitrates when cadmium is present and to allow analysis at very low concentrations without the removal of oxygen. The deposition and dissolution of Pb²⁺ and Cd²⁺ proceed at underpotential (UPD) on both electrodes. The UPD properties of the deposits are the main factor determining the analytical characteristics of the ASV method and are strongly affected by the type and concentration of the electrolyte. The effects of anions (Cl⁻, Br⁻, SO₄²⁻, NO₃⁻) and acids (HNO₃, HClO₄, H₂SO₄, HCl) are shown. The two electrodes complement each other and, in addition, enable the qualitative identification of Pb²⁺ and Cd²⁺, since the peaks appear in opposite order on the two electrodes. Analysis of mixtures of the two analytes is restricted on gold but not on silver. At gold the two peaks overlap: (i) at concentrations of cadmium higher than 250 nM at deposition times greater than 30 s, (ii) in the presence of copper at concentrations higher than 1 μM, and (iii) in the presence of Triton X-100 at concentrations above 10 mg/l. The repeatability at 10 nM analyte is better than 2.5%. The detection limits for Pb²⁺ and Cd²⁺ at 120 s deposition time and 3500 rpm rotation rate are: dl_Pb/Ag=0.04 nM; dl_Cd/Ag=0.7 nM; dl_Pb/Au=0.1 nM; dl_Cd/Au=0.3 nM. The analysis of lead and cadmium in natural waters has been performed.     

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at −0.3 V versus Ag/AgCl_sat a linear range from 7.5 × 10⁻⁸ to 2.5 × 10⁻⁶ mol L⁻¹ with detection limit of 3.1 × 10⁻⁸ mol L⁻¹ was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu²⁺ and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu²⁺ in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods.     

A validated stripping voltammetric procedure for quantification of the anti-hypertensive and benign prostatic hyperplasia drug terazosin in tablets and human serum

The electrochemical behavior of terazosin at the hanging mercury drop electrode was studied in Britton-Robinson buffer (pH 2-11), acetate buffer (4.5-5.5), and in 0.1 M solution of each of sodium sulfate, sodium nitrate, sodium perchlorate and potassium chloride as supporting electrolytes. The square-wave adsorptive cathodic stripping voltammogram of terazosin exhibited a single well-defined two-electron irreversible cathodic peak which may be attributed to the reduction of CO double bond of the drug molecule. A fully validated, simple, high sensitive, precise and inexpensive square-wave adsorptive cathodic stripping voltammetric procedure was described for determination of terazosin in bulk form, tablets and human serum. A mean recovery for 1×10⁻⁸ M terazosin in bulk form, following preconcentration onto the hanging mercury drop electrode for 60 s at a −1.0 V (versus Ag/AgCl/KCl_s), of 99±0.7% (n=5) was obtained. Limits of detection (LOD) and quantitation (LOQ) of 1.5×10⁻¹¹ and 5×10⁻¹¹ M bulk terazosin were achieved, respectively. The proposed procedure was successfully applied to determination of the drug in its Itrin^® tablets and human serum samples. The achieved LOD and LOQ of the drug in human serum samples were 5.3×10⁻¹¹ and 1.8×10⁻¹⁰ M THD, respectively. The pharmacokinetic parameters of the drug in human plasma were estimated as: C_max=77.5 ng ml⁻¹, t_max=1.75 h, AUC_0-t=602.3 ng h ml⁻¹, K_e=0.088 h⁻¹ and t_1/2=11.32 h) which are favorably compared with those reported in literature.     

H-point standard addition method in the analysis by differential pulse anodic stripping voltammetry Simultaneous determination of lead and tin

The applicability of H-point standard addition method (HPSAM) to the resolving of overlapping differential pulse anodic stripping voltammetric peaks corresponding to the oxidation of lead and tin is verified. The results show that the H-point standard addition method is suitable for the simultaneous determination of lead and tin in aqueous media. The results of applying the H-point standard addition method showed that Sn²⁺ and Pb²⁺ could be determined simultaneously with the concentration ratios of Sn²⁺ to Pb²⁺ varying from 1:5 to 10:1 in the mixed sample. The proposed method has been successfully applied to the simultaneous determination of lead in the presence of tin in some synthetic samples. Moreover, the applicability of the method was demonstrated by the recovery of lead in a canned soft drink sample.     

Electrochemical and microfabrication strategies for remotely operated smart chemical sensors: Application of anodic stripping coulometry to calibration-free measurements of copper and mercury

Remote unattended sensor networks are increasingly sought after to monitor the drinking water distribution grid, industrial wastewater effluents, and even rivers and lakes. One of the biggest challenges for application of such sensors is the issue of in-field device calibration. With this challenge in mind, we report here the use of anodic stripping coulometry (ASC) as the basis of a calibration-free micro-fabricated electrochemical sensor (CF-MES) for heavy metal determinations. The sensor platform consisted of a photo-lithographically patterned gold working electrode on SiO₂ substrate, which was housed within a custom stopped-flow thin-layer cell, with a total volume of 2–4 μL. The behavior of this platform was characterized by fluorescent particle microscopy and electrochemical studies utilizing Fe(CN)₆^3−/4− as a model analyte. The average charge obtained for oxidation of 500 μM ferrocyanide after 60 s over a 10 month period was 176 μC, corresponding to a volume of 3.65 μL (RSD = 2.4%). The response of the platform to copper concentrations ranging from 50 to 7500 ppb was evaluated, and the ASC results showed a linear dependence of charge on copper concentrations with excellent reproducibility (RSD ≤ 2.5%) and accuracy for most concentrations (≤5–10% error). The platform was also used to determine copper and mercury mixtures, where the total metallic content was measurable with excellent reproducibility (RSD ≤ 4%) and accuracy (≤6% error).