Bismuth Film along with dsDNA-Modified Electrode Surfaces as Promising (bio)Sensors in the Analysis of Heavy Metals in Soils.

Heavy metals constitute pollutants that are particularly common in air, water, and soil. They are present in both urban and rural environments, on land, and in marine ecosystems, where they cause serious environmental problems since they do not degrade easily, remain almost unchanged for long periods, and bioaccumulate. The detection and especially the quantification of metals require a systematic process. Regular monitoring is necessary because of seasonal variations in metal levels. Consequently, there is a significant need for rapid and low-cost metal determination methods. In this study, we compare and analytically validate absorption spectrometry with a sensitive voltammetric method, which uses a bismuth film-plated electrode surface and applies stripping voltammetry. Atomic absorption spectroscopy (AAS) represents a well-established analytical technique, while the applicability of anodic stripping voltammetry (ASV) in complicated sample matrices such as soil samples is currently unknown. This sample-handling challenge is investigated in the present study. The results show that the AAS and ASV methods were satisfactorily correlated and showed that the metal concentration in soils was lower than the limit values but with an increasing trend. Therefore, continuous monitoring of metal levels in the urban complex of a city is necessary and a matter of great importance. The limits of detection of cadmium (Cd) were lower when using the stripping voltammetry (SWASV) graphite furnace technique compared with those obtained with AAS when using the graphite furnace. However, when using flame atomic absorption spectroscopy (flame-AAS), the measurements tended to overestimate the concentration of Cd compared with the values found using SWASV. This highlights the differences in sensitivity and accuracy between these analytical methods for detecting Cd. The SWASV method has the advantage of being cheaper and faster, enabling the simultaneous determination of heavy elements across the range of concentrations that these elements can occur in Mediterranean soils. Additionally, a dsDNA biosensor is suggested for the discrimination of Cu(I) along with Cu(II) based on the oxidation peak of guanine, and adenine residues can be applied in the redox speciation analysis of copper in soil, which represents an issue of great importance.

Determination of indium by adsorptive stripping voltammetry at the bismuth film electrode using combined electrode system facilitating medium exchange.

A novel method of determining indium has been described in this article which uses adsorptive stripping voltammetry (AdSV) and 4-(2-pyridylazo)-resorcinol (PAR) as a chelating agent or as the preconcentration agent. The measurements were performed using square-wave voltammetry by using a combined electrode system, which allows for preconcentration and stripping without opening the circuit. Ex situ plated bismuth film electrode (BiFE) was used as the working electrode. A potential-time program was developed for the inversion cycle stages based on the various factors that affect the magnitude of the inversion signal. The calibration curve was linear in a concentration range of 2·10-7 to 4·10-6 М when the pH is 4.8, accumulation potential is -700 mV, and PAR concentration is 1·10-4 M. The detection limit for the 3σ criterion with an accumulation time of 120 s was 3.5·10-9 М. Several interferences caused by Tl(I), Zn(II), Cu(II), Pb(II), Co(II), Ni(II), Mn(II), Fe(III), Cr(III) ions have been studied, and it has been shown that medium exchange procedure can effectively eliminate some interferences. It was demonstrated that the method can be applied to the determination of indium in tap water and in ITO glass sample.

An Electrochemical Sensor for the Determination of Trace Concentrations of Cadmium, Based on Spherical Glassy Carbon and Nanotubes.

The practical application of a novel, eco-friendly electrochemical sensor based on low-dimensional structures, spherical glassy carbon microparticles, and multiwall carbon nanotubes is described. This sensor, modified with a bismuth film, was used for the determination of Cd(II) by the anodic stripping voltammetric method. The instrumental and chemical factors influencing the sensitivity of the procedure were thoroughly investigated and their most favorable values were selected (acetate buffer solution pH = 3 ± 0.1; 0.15 mmol L-1 Bi(III); activation potential/time: -2 V/3 s; accumulation potential/time: -0.9 V/50 s). Under the selected conditions, the method exhibited linearity in the range of 2 × 10-9 to 2 × 10-7 mol L-1 Cd(II) with a detection limit of 6.2 × 10-10 mol L-1 Cd(II). The results obtained also showed that the application of the sensor for Cd(II) detection did not experience any significant interference in the presence of a number of foreign ions. The applicability of this procedure was evaluated using TM-25.5 Environmental Matrix Reference Material and SPS-WW1 Waste Water Certified Reference Material as well as river water samples through addition and recovery tests.

Ultra-trace levels voltammetric determination of Pb2+ in the presence of Bi3+ at food samples by a Fe3O4@Schiff base Network1 modified glassy carbon electrode.

In this research, a highly sensitive electrochemical sensor was developed for the square wave anodic stripping voltammetric determination of Pb2+ at ultra-trace levels. A Glassy carbon electrode was modified with an in-situ electroplated bismuth film and the nanocomposite of a recently synthesized melamine based covalent organic framework (schiff base network1 (SNW1)) and Fe3O4 nanoparticles (Fe3O4@SNW1). The obtained results exhibit clearly that combination of Fe3O4@SNW1 and in-situ electroplated bismuth film enhances the sensitivity of the modified electrode towards Pb2+ remarkably. A Plackett-Burman design was implemented for screening experimental factors to specify the significant variables influencing the sensitivity of the electroanalytical method. Afterward, the effective factors were optimized using Box-Behnken design (BBD). Under optimized conditions, the proposed electrode showed a linear response towards Pb2+ in the concentration range of 0.003-0.3 µmol L-1 with the detection limit of 0.95 nmol L-1. The selectivity of the fabricated electrode towards different ionic species were checked out and no serious interference was observed. At the end, the application of the designed sensor in the determination of Pb2+ at 10 different edible specimens were investigated and the obtained recovery values were in the range of (95.56-106.64%) indicating the successful performance of the designed sensor.

Electrochemical evaluation of the desloratadine at bismuth film electrode in the presence of cationic surfactant: Highly sensitive determination in pharmaceuticals and human urine by Linear sweep-cathodic stripping voltammetry.

In this study, the electrochemical properties of desloratadine, which is in the second generation antihistamines group, were determined by bismuth film electrode (BiFE) in aqueous and aqueous/surfactant solutions. This compound gave an irreversible and diffusion-controlled reduction peak at about -1.65 V by cyclic voltammetry. It was found that the addition of cationic surfactants (cetyltrimethylammonium bromide (CTAB) increased the reduction current signal of desloratadine, while anionic (sodium dodecylsulfate (SDS) and nonionic (Tween 80) surfactants were found to have an adverse effect. Using linear sweep-cathodic stripping voltammetry, the analytical signal showed a linear correlation with a concentration of 0.1 to 4 µM in 0.04 M Britton-Robinson solution (pH = 8.0) in the presence of 5 mM CTAB, while the detection limit was calculated to be 11.70 nM (3.64 µgL-1). This method has been successfully applied for the quantitation of desloratadine in pharmaceutical and urine samples without the need for any separation.

Bismuth Film-Coated Gold Ultramicroelectrode Array for Simultaneous Quantification of Pb(II) and Cd(II) by Square Wave Anodic Stripping Voltammetry.

The widespread presence of heavy metals in drinking water sources arises as a major health concern, particularly in developing countries. The development of low-cost and reliable detection techniques is identified as a societal need to provide affordable water quality control. Herein, a bismuth film-coated gold ultramicroelectrode array (BF-UMEA) was used for the detection of Pb(II) and Cd(II) in water samples via square wave anodic stripping voltammetry (SWASV). Experimental parameters such as deposition time, Bi(III) concentration, acetate buffer concentration, pH, square wave frequency, amplitude, and step potential were all varied to determine their effects on the current peak intensities of the target metal ions. Ten-fold excess in the concentration of interferences was found to cause a decrease in the stripping peak areas of Cd(II) and Pb(II) in the following order of magnitude: benzene < NaCl < Ni(II) < Cu(II). Using Box-Behnken design, the optimum SWASV parameters that provided maximum current peak areas were 14.76 Hz (frequency), 50.10 mV (amplitude), and 8.76 mV (step potential). The limits of detection of the as-prepared BF-UMEA were 5 and 7 µg L-1 for Pb(II) and Cd(II), respectively. These results demonstrate the potential use of a BF-UMEA in SWASV for the trace quantification of Pb(II) and Cd(II) in water samples.

Nanostructured Bismuth Film Electrode for Detection of Progesterone.

Progesterone is an important hormone responsible, among others, for maintaining pregnancy via inhibition of uterus muscles activity; thus, following its concentration levels in pregnant women is of immense importance in the endeavor to prevent premature birth. In this work, the nanostructured bismuth film electrode (nsBiFE) was studied for detection of progesterone in neutral medium. Due to the ability to accumulate progesterone at the nsBiFE, the adsorptive cathodic stripping voltammetry was beneficially exploited. The nsBiFE was prepared on the surface of a glassy carbon supporting electrode and several parameters influencing the detection of progesterone were investigated. The nsBiFE exhibited superior electroanalytical characteristics in comparison to other bismuth-based electrodes and unmodified glassy carbon electrode together with satisfactory response toward low concentrations of progesterone, which are consistent with clinically significant levels.

Ultrasensitive hexavalent chromium determination at bismuth film electrode prepared with mediator.

A bismuth film electrode prepared in situ with a reversibly deposited mediator (Zn) applied for ultrasensitive determination of Cr(VI) using differential pulse catalytic adsorptive stripping voltammetry is presented. The optimization of experimental conditions such as composition of the supporting electrolyte, potential and time of bismuth film formation as well as analyte accumulation, and DP mode parameters is reported. For 180 s accumulation time, very low limits of detection and quantification of Cr(VI) were obtained, with 5.8 × 10-14 and 1.9 × 10-13 mol L-1, respectively. The relative standard deviation for 5.0 × 10-13 mol L-1 of Cr(VI) was 3.9% (n = 5). Finally, the proposed procedure was applied to determine Cr(VI) in the certified reference materials - NASS-6 (seawater), SLEW-3 (estuarine water) and TMRAIN-04 (rainwater) - as well as in river water samples. Furthermore, the obtained results show that the proposed voltammetric procedure employing the bismuth film electrode prepared with mediator appears to form a very promising tool for the speciation of chromium at ultratrace level.

A detailed electrochemical impedance spectroscopy study of a bismuth-film glassy carbon electrode for trace metal analysis.

A systematic electrochemical impedance spectroscopy (EIS) analysis at different potentials of an in situ-prepared bismuth-film glassy carbon electrode (BiFE) in 0.1 M acetate buffer solution is reported. This electrode is employed in the square-wave anodic stripping voltammetry (SWASV) technique for the determination of trace amounts of the heavy metals Zn, Cd, and Pb. The method was first validated for detection limit, linear range, sensitivity, precision and accuracy to clearly prove the superior action of BiFE compared with the bare glassy carbon electrode (GCE). Next, in order to investigate the characteristics of this sensor, EIS measurements were carried out at slightly more negative potentials than the potentials at which each individual stripping signal is detected, after the deposition step at different deposition potentials. For comparison, EIS measurements were also performed at open circuit potential. The studied trace metal concentration range (5-20 ppb) did not significantly influence the capacitive and resistive behaviour of the BiFE which explains why the performance of this sensor is superior compared with the bare GCE. The higher sensitivity of the SWASV method for BiFE compared with the bare GCE was explained by the lower polarisation resistance values of the former. Moreover, the potential of zero charge was also determined, and an explanation whether the system is under kinetic- and/or diffusion-controlled process is given.

Direct Quantification of Cd2+ in the Presence of Cu2+ by a Combination of Anodic Stripping Voltammetry Using a Bi-Film-Modified Glassy Carbon Electrode and an Artificial Neural Network.

Abstract: In this study, a novel method based on a Bi/glassy carbon electrode (Bi/GCE) for quantitatively and directly detecting Cd2+ in the presence of Cu2+ without further electrode modifications by combining square-wave anodic stripping voltammetry (SWASV) and a back-propagation artificial neural network (BP-ANN) has been proposed. The influence of the Cu2+ concentration on the stripping response to Cd2+ was studied. In addition, the effect of the ferrocyanide concentration on the SWASV detection of Cd2+ in the presence of Cu2+ was investigated. A BP-ANN with two inputs and one output was used to establish the nonlinear relationship between the concentration of Cd2+ and the stripping peak currents of Cu2+ and Cd2+. The factors affecting the SWASV detection of Cd2+ and the key parameters of the BP-ANN were optimized. Moreover, the direct calibration model (i.e., adding 0.1 mM ferrocyanide before detection), the BP-ANN model and other prediction models were compared to verify the prediction performance of these models in terms of their mean absolute errors (MAEs), root mean square errors (RMSEs) and correlation coefficients. The BP-ANN model exhibited higher prediction accuracy than the direct calibration model and the other prediction models. Finally, the proposed method was used to detect Cd2+ in soil samples with satisfactory results.

A simple stripping voltammetric method for the determination of a new anticancer prodrug in serum.

The determination of ethyl [4-oxo-8-(3-chlorophenyl)-4,6,7,8-tetrahydroimidazo[2,1-c][1,2,4]triazin-3-yl]acetate (ETTA), a new anticancer prodrug, using adsorptive stripping voltammetry (AdSV) was described for the first time. This method is based on adsorptive/reductive behaviour of ETTA at an in situ plated bismuth film electrode (BiFE) as a sensor. A number of experimental variables (e.g., a composition and pH of the supporting electrolyte, the conditions of bismuth film deposition, an accumulation potential and time, the scan rate, etc.) were thoroughly studied in order to achieve a high sensitivity. Experimental results under optimized conditions revealed an excellent linear correlation between the monitored voltammetric peak current and the ETTA concentration in the range of 2-50µgL-1 following an accumulation time of 300s. The limit of detection (LOD) for ETTA following 300s of an accumulation time was 0.4µgL-1. The proposed facile, sensitive and inexpensive method was successfully applied to the determination of ETTA in serum. The investigated prodrug was extracted from serum using SPE method.

Synthesis of a novel electrode material containing phytic acid-polyaniline nanofibers for simultaneous determination of cadmium and lead ions.

The development of nanostructured conducting polymers based materials for electrochemical applications has attracted intense attention due to their environmental stability, unique reversible redox properties, abundant electron active sites, rapid electron transfer and tunable conductivity. Here, a phytic acid doped polyaniline nanofibers based nanocomposite was synthesized using a simple and green method, the properties of the resulting nanomaterial was characterized by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A glassy carbon electrode modified by the nanocomposite was evaluated as a new platform for the simultaneous detection of trace amounts of Cd2+ and Pb2+ using differential pulse anodic stripping voltammetry (DPASV). The synergistic contribution from PANI nanofibers and phytic acid enhances the accumulation efficiency and the charge transfer rate of metal ions during the DPASV analysis. Under the optimal conditions, good linear relationships were obtained for Cd2+ in a range of 0.05-60 µg L-1, with the detection limit (S/N = 3) of 0.02 µg L-1, and for Pb2+ in a range of 0.1-60 µg L-1, with the detection limit (S/N = 3) of 0.05 µg L-1. The new electrode was successfully applied to real water samples for simultaneous detection of Cd2+ and Pb2+ with good recovery rates. Therefore, the new electrode material may be a capable candidate for the detection of trace levels of heavy metal ions.

Optimization of Stripping Voltammetric Sensor by a Back Propagation Artificial Neural Network for the Accurate Determination of Pb(II) in the Presence of Cd(II).

An easy, but effective, method has been proposed to detect and quantify the Pb(II) in the presence of Cd(II) based on a Bi/glassy carbon electrode (Bi/GCE) with the combination of a back propagation artificial neural network (BP-ANN) and square wave anodic stripping voltammetry (SWASV) without further electrode modification. The effects of Cd(II) in different concentrations on stripping responses of Pb(II) was studied. The results indicate that the presence of Cd(II) will reduce the prediction precision of a direct calibration model. Therefore, a two-input and one-output BP-ANN was built for the optimization of a stripping voltammetric sensor, which considering the combined effects of Cd(II) and Pb(II) on the SWASV detection of Pb(II) and establishing the nonlinear relationship between the stripping peak currents of Pb(II) and Cd(II) and the concentration of Pb(II). The key parameters of the BP-ANN and the factors affecting the SWASV detection of Pb(II) were optimized. The prediction performance of direct calibration model and BP-ANN model were tested with regard to the mean absolute error (MAE), root mean square error (RMSE), average relative error (ARE), and correlation coefficient. The results proved that the BP-ANN model exhibited higher prediction accuracy than the direct calibration model. Finally, a real samples analysis was performed to determine trace Pb(II) in some soil specimens with satisfactory results.

Determination of Sb(III) using an ex-situ bismuth screen-printed carbon electrode by adsorptive stripping voltammetry.

The determination of Sb(III) on an ex-situ bismuth screen-printed carbon electrode (ex-situ BiSPCE) by means of adsorptive stripping voltammetry (AdSV) using quercetin-5'-sulfonic acid as chelating agent was optimized. The effect of different experimental parameters such pH, ligand concentration (CQSA), accumulation potential (Eacc) and accumulation time (tacc) were studied to obtain a wide linear range, the highest sensitivity and the lowest detection limit. Ex-situ BiSPCE was analytically compared with a sputtered bismuth screen-printed electrode (BispSPE) under optimal conditions. The obtained analytical parameters suggest that ex-situ BiSPCE behaves much better than BispSPE and the first was selected for this study. Optimal parameters were pH=4.6; CQSA=10.0 to 20.0×10(-6)molL(-1); Eacc=-0.5V and tacc=60s. Peak area is proportional to Sb(III) concentration up to 100.0µgL(-1) (tacc 60s) and 45.0µgL(-1) (tacc 120s) range, with detection limits of 1.2µgL(-)(1) (tacc 60s) and 0.8µgL(-1) (tacc 120s). The relative standard deviation for a Sb(III) solution (20.0µgL(-1)) was 3.9% for ten successive assays. Thus, the effect of various interfering metal ions was studied and the methodology was validated using a spiked groundwater reference material with very satisfactory results.

Environmentally-friendly in situ plated bismuth-film electrode for the quantification of the endocrine disruptor parathion in skimmed milk.

An in situ bismuth-film electrode (BiFE) together with square-wave cathodic voltammetry (SWCV) was used to determine the concentration of the endocrine disruptor parathion in skimmed milk. The experimental conditions (deposition time, deposition potential and Bi (III) concentration) were optimized for the preparation of the BiFE. A glassy carbon electrode was used as the substrate. The selection of the chemical composition of the supporting electrolyte and the solution pH was aimed at improving the reduction of parathion at the BiFE surface. In addition, the parameters of the square-wave cathodic voltammetry were adjusted to improve the sensor performance. A cathodic current identified at -0.523 V increased linearly with the parathion concentration in the range of 0.2-2.0 µmol L(-1) (R=0.999). The sensitivity of the calibration curve obtained was 4.09 µA L µmol(-1), and the limits of detection (LOD) and quantification (LOQ) were 55.7 nmol L(-1) and 169.0 nmol L(-1), respectively. The performance of the sensor was tested using a sample of skimmed milk with parathion added. The same determination was carried out by UV-vis spectroscopy and the results obtained were used for the statistical evaluation of the data obtained.

Lead migration from toys by anodic stripping voltammetry using a bismuth film electrode.

Metals may be released from toys via saliva during mouthing, via sweat during dermal contact, or via gastric and intestinal fluids after partial or whole ingestion. In this study, we determined the lead migration from toys bought on the Portuguese market for children below 3 years of age. The lead migration was performed according to the European Committee for Standardization EN 71-3, which proposes a 2-hour migration test that simulates human gastric conditions. The voltammetric determination of migrated lead was performed by anodic stripping voltammetry (ASV) at a bismuth film electrode (BiFE). For all the analyzed toys, the values of migrated lead did not exceed the limits imposed by the European Committee for Standardization EN 71-3 (90 mg kg-1) and by the EU Directive 2009/48/EC (13.5 mg kg-1) on the safety of toys.

Determination of trace amounts of Ga(III) by adsorptive stripping voltammetry with in situ plated bismuth film electrode.

The determination of trace gallium using adsorptive stripping voltammetry at an in situ plated bismuth film electrode was described. The method was based on simultaneous film formation and the Ga(III)-cupferron complex preconcentration at -0.65 V and its cathodic stripping during the potential scan. The effect of Bi(III) and cupferron concentration, the influence of deposition potential and time, and the scan rate on the determination of Ga(III) were studied. A linear response in the concentration range of 3×10(-10) to 3×10(-7) mol L(-1) (r=0.998) was obtained with detection limit of 1.05×10(-10) mol L(-1) using accumulation time of 180 s. Finally, the bismuth film electrode was successfully applied for the determination of Ga(III) in certified reference material seawater NASS-5 with satisfactory results.

A thermostated electrochemical flow cell with a coupled bismuth film electrode for square-wave anodic stripping voltammetric determination of cadmium(II) and lead(II) in natural, wastewater and tap water samples.

In order to reduce the sample consumption and waste generation for electrochemical purposes, a screen-printed electrode (SPE) used for electrodeposition of bismuth film (SPE-BiFE) and a thermostated electrochemical flow cell (EFC) were developed. The SPE-BiFE with the EFC was employed to determine Cd(2+) and Pb(2+) ions in natural, wastewater and tap water samples by square-wave anodic stripping voltammetry (SWASV). For this, the flow-batch analysis (FBA) approach based on solenoid micro-pumps and three-way valves was developed to carry out a fully automated procedure with temperature control. Furthermore, the FBA and the SWASV parameters were optimized, on line simultaneous determination of Cd(2+) and Pb(2+) ions was performed and two analytical curves were linearly acquired in the concentration ranges from 6.30 to 75.6µg L(-1) and from 3.20 to 38.4µg L(-1), respectively. Moreover, limits of detection of 0.60µg L(-1) and 0.10µg L(-1) for Cd(2+) and Pb(2+), respectively, were obtained. Studies of precision for the same SPE-BiFE and repeatability for five built SPE-BiFE were carried out for Cd(2+) and Pb(2+) ion measurements and RSD of 4.1% and 2.9% (n=3) with repeatabilities (n=5) of 6.5% and 8.0% were respectively obtained for both analytes. Besides, a low consumption of 700µL of reagents and a sampling frequency of 13h(-1) were acquired. Simplicity, fast response, accuracy, high portability, robustness and suitability for in loco analyses are the main features of the proposed electroanalytical method.

Mutual Influence of Lead and Cadmium Ions on Bismuth Film Electrode / 分析化学

The mutual influence of lead and cadmium ions on “in-situ” bismuth film coated glassy carbon electrode was demonstrated using different concentration target ions by changing ratio between Pb2+ and Cd2+. It is found that the presence of coexisting ions can have an influence on the detection of target ions. Especially for the detection of Cd2+, the existence of Pb2+ can be beneficial for the deposition of Cd due to the more positive deposition potentials. And the analytical performances of Cd2+and Pb2+ were obtained. The detection limit is 0. 5 μg/L towards Pb2+ with a linear range from 1-80 μg/L using 60 s deposition time. The resulting calibration plots of Cd2+ are linear over the range from 1-25 and 30-200 μg/L with the detection limit of 1 μg/L using 120 s deposition time. The bismuth film was finally employed to determine the Pb2+and Cd2+in real sample with good satisfied results.

A Nafion-coated bismuth film electrode for the determination of heavy metals in vegetable using differential pulse anodic stripping voltammetry: An alternative to mercury-based electrodes.

Mercury electrodes have been traditionally employed for achieving high reproducibility and sensitivity of the stripping technique. However, new alternative electrode materials are highly desired because of the toxicity of mercury. Bismuth is an electrode material characterized by its low toxicity and its ability to form alloys with some metals such as cadmium, lead and zinc, allowing their preconcentration at the electrode surface. In this work, we reported the simultaneous determination of Pb(II), Cd(II) and Zn(II) at the low µg/l concentration levels by differential pulse anodic stripping voltammetry (DPASV) on a Nafion-coated bismuth film electrode (NCBFE) plated in situ, and investigated the application of NCBFE to heavy metals analysis in vegetable samples. The analytical performance of NCBFE was evaluated for simultaneous determination of Pb(II), Cd(II) and Zn(II) in non-deaerated solution, with the limits of determination of 0.30µg/l for Zn, 0.17µg/l for Cd and Pb at a preconcentration time of 180s. High reproducibility for NCBFE was indicated from the relative standard deviations of 2.4% for Pb, 2.0% for Cd and 3.4% for Zn at the 15µg/l level (n=15). The NCBFE was successfully applied to determine Pb and Cd in vegetable samples, and the results were in agreement with those of graphite furnace atomic absorption spectrometry (GFAAS).