Study of Metallothionein Modified Electrode Surface Behavior in the Presence of Heavy Metal Ions‐Biosensor

An increasing concentration of heavy metals in the environment is a serious problem for human and animal health protection and production of foodstuffs in many countries around the world. The aim of this paper was to suggest a new heavy metal biosensor based on interaction of metals (cadmium and zinc) with metallothionein, which belongs to group of intracellular, high molecular and cysteine‐rich proteins binding heavy metals, using adsorptive transfer stripping (AdTS) differential pulse voltammetry (DPV). Primarily, we studied the electrochemical behavior of MT on the surface of hanging mercury drop electrode by AdTS DPV. Perfect coverage of the electrode surface – forming of the surface assembled monolayer – was probably reached in about 240 s for 10 μM protein concentration. The detection limits of the selected heavy metals (cadmium and zinc), which were analyzed in the presence of the basic electrolyte – 0.5 M NaCl (pH 6.4), were 250 fmol and 350 fmol in 5 μL drop, respectively. In addition, we applied the biosensor to analyze heavy metals in human body liquids (human blood serum and human urine) and to compare with differential pulse anodic stripping voltammetry.     

Optimization and validation of an automated voltammetric stripping technique for ultratrace metal analysis

A new automated batch method for the determination of ultratrace metals (nanogram per liter level) was developed and validated. Instrumental and chemical parameters affecting the performance of the method were carefully assessed and optimized. A wide range of voltammetric methods under different chemical conditions were tested. Cadmium, lead and copper were determined by anodic stripping voltammetry (ASV), while nickel, cobalt, rhodium and uranium by adsorptive cathodic stripping voltammetry (AdCSV). The figures of merit of all of these methods were determined: very good precision and accuracy were achieved, e.g. relative percentage standard deviation in the 4-13% for ASV and 2-5% for AdCSV.The stripping methods were applied to the determination of cadmium, lead, copper, nickel, cobalt, rhodium and uranium in lake water samples and the results were found to be comparable with ICP-MS data.     

Characterisation of Screen-Printed Electrodes for Detection of Heavy Metals

 The characterisation of disposable screen-printed electrodes for stripping analysis is described. The graphite surface of the working electrode is used as substrate for plating a thin mercury film, which allows the electrochemical preconcentration of heavy metals. Optimisation procedures and experimental results are presented. Detection limits around the ppb level were obtained for different metals [Pb(II), Cd(II), Cu(II)]. Received June 6, 1998. Revision November 10, 1988.     

Differential pulse anodic stripping voltammetry detection of metallothionein at bismuth film electrodes

As a representation of metalloproteins, metallothionein (MT), which plays important biological and environmental roles such as in the metabolism and detoxification of some metals, was detected at bismuth film electrode (BiFE) by differential pulse anodic stripping voltammetry (DPASV). In pH 2–5.5, two well-defined anodic peaks were produced and attributed to the Zn²⁺ and Cd²⁺ inherent to MT. The calibration plot of DPASV peak currents for Cd²⁺ inherent to MT versus MT concentrations showed a good linearity with a detection limit of 3.86 × 10⁻⁸ mol/L for MT. As a non-toxic excellent electrode material, BiFE shows good performance for detecting MT, and is expected to find further applications in the studies of many other metalloproteins.     

A Robust Electrochemical Sensor Based on Butterfly-shaped Silver Nanostructure for Concurrent Quantification of Heavy Metals in Water Samples

Heavy metals in drinking water have become a severe threat to human health. Detection of heavy metals has been achieved by electrochemical sensors that are modified with complex nanocomposites; however, reproducibility of these sensors is still a big challenge when applied in commercial settings. Here, a simple, very robust, and sensitive electrochemical sensor based on a screen-printed carbon electrode modified with butterfly-shaped silver nanostructure (AgNS/SPCE) has been developed for the concurrent determination of cadmium (II), lead (II), copper (II), and mercury (II) in water samples. The electrochemical behavior of the modified electrodes was investigated using cyclic voltammetry and differential pulse anodic stripping voltammetry. The AgNS/SPCE showed distinct peak potentials and a significant increase in the peak currents for all heavy metals, attributed to the high electrical conductivity and electrocatalytic activity of the synthesized butterfly-shaped AgNS. Moreover, the excellent stability and sensitivity towards simultaneous quantification of heavy metals have been obtained with detection limits of 0.4 ppb, 2.5 ppb, 7.3 ppb, and 0.7 ppb for Cd (II), Pb (II), Cu (II), and Hg (II), respectively. Besides, the constructed sensor was successfully applied to simultaneously quantify target heavy metals in spiked water samples. Owing to excellent sensitivity, high robustness, affordability, and fast response, the presented electrochemical sensor could be incorporated into a portable and miniaturized potentiostat device, making it a promising method for on-site water analysis.     

Direct and simultaneous voltammetric analysis of heavy metals in tap water samples at Assiut city: an approach to improve the analysis time for nickel and cobalt determination at mercury film electrode

Tap water samples (Assiut city, lie in the middle north of upper Egypt, approx. 370 km from Cairo, January-March, 2002) were taken from the eight sampling sites of different locations at Assiut city. The samples are analyzed to determine the total content of cadmium, copper, lead and zinc by differential pulse anodic stripping voltammetry (DPASV) while nickel and cobalt are determined by a new simple differential pulse adsorptive stripping voltammetry (DPAdSV), using dimethylglyoxime (DMG) as the complexing agent. This method uses sodium sulfite as the supporting electrolyte, which facilitates the removal of oxygen interference without the traditional necessity of purging with inert gas. The effect of various parameters was studied using DPASV (for Cd, Pb, Cu and Zn) and AdSV (for Ni and Co) methods. Subsequently, under the so found experimental conditions, the stability of calibration curves and the detection limits (μg/l) have been determined. The data achieved (for all metals utility) are comparable to those measured by the graphite furnace atomic absorption spectrophotometric (GF-AAS) method. The effects of the interferences between these metal ions have been investigated. Moreover, the effect of storage was discussed and the obtained results were compared favorably with standard official methods. Statistical analysis of the database exhibits applicability and the accuracy of the techniques. The results obtained from the two techniques (Voltammetry and GF-AAS) are in very good agreements in the most tap water samples.     

Carbon Nanotubes Heavy Metal Detection with Stripping Voltammetry: A Review Paper

The challenge of heavy metal detection for environmental, industrial and medical purposes has led to the development of many analytical techniques. Stripping voltammetry is a very sensitive electrochemical method and has been widely used for heavy metal detection. Carbon nanotubes, a well‐studied carbon material with physical and chemical properties suited for electrode material is commonly employed for sensitive and selective metal detection in electrochemistry. This article reviews the recent (2011–2016) applications of carbon nanotubes as an electrode or electrode surface modifier for heavy metals detection with stripping voltammetry.     

Manganese Detection Using Stencil‐printed Carbon Ink Electrodes on Transparency Film

Mn concentrations were determined using square‐wave cathodic stripping voltammetry (CSV) with inexpensive, stencil‐printed carbon ink electrodes generated on polypropylene transparency films. Using an optimized pH 5 ammonium acetate buffer and addition of 1,4‐benzoquinone, a detection limit as low as 500 nM (30 ppb) was achieved. Addition of 1,4‐benzoquinone improved peak potential reproducibility and height, while addition of 3.5 % w/w sodium chloride to the background solution approximately doubled the sensitivity (μA/ppm). Tolerance tests with interfering metals were conducted and the method was found to be resilient to chromium(VI), iron(III), magnesium(II), nickel(II), and zinc(II), but susceptible to aluminum(III), copper(II), iron(II), and lead(II) at concentration ratios at or below one. This technique was successfully used to measure Mn levels in yerba mate and green tea samples as an example application.     

Poly(ester sulphonic acid) coated mercury thin film electrodes: characterization and application in batch injection analysis stripping voltammetry of heavy metal ions

Mercury-thin film electrodes coated with a thin film of poly(ester sulphonic acid) (PESA) have been investigated for application in the analysis of trace heavy metals by square wave anodic stripping voltammetry using the batch injection analysis (BIA) technique. Different polymer dispersion concentrations in water/acetone mixed solvent are investigated and are characterised by electrochemical impedance measurements on glassy carbon and on mercury film electrodes. The influence of electrolyte anion, acetate or nitrate, on polymer film properties is demonstrated, acetate buffer being shown to be preferable for stripping voltammetry applications. Although stripping currents are between 30 and 70% less at the coated than at bare mercury thin film electrodes, the influence of model surfactants on stripping response is shown to be very small. The effect of the composition of the modifier film dispersion on calibration plots is shown; however, detection limits of around 5 nM are found for all modified electrodes tested. This coated electrode is an alternative to Nafion-coated mercury thin film electrodes for the analysis of trace metals in complex matrices, particularly useful when there is a high concentration of non-ionic detergents.     

Electrochemical Sample Preparation for the Voltammetric Determination of Heavy-Metal Ions in Wine

An original, simple, and rapid method consuming little labor and eliminating the contamination of a sample and the loss of analytes is proposed for the electrochemical preparation of wine samples. The time of electrochemical sample preparation (ECSP) is no longer than 10 min. A four-electrode single-compartment electrolyzer allows all stages of voltammetric analysis (electrochemical sample preparation, electrochemical preconcentration and determination) to be carried out continuously. The processes occurring at electrodes at different stages of analysis are described. The concentrations of heavy metals determined in wines by stripping voltammetry (SVA) and atomic absorption spectroscopy (AAS) are compared.     

Voltammetric method for the determination of Zn,Cd, Pb,Cu and Ni in interstitial water

To determine heavy metals in interstitial water from Baltic sea sediments a sampling method with subsequent voltammetric determination is described. Copper, lead, zinc and cadmium are determined in the UV-digested samples of interstitial water by differential pulse anodic stripping voltammetry while nickel is determined by adsorption voltammetry. The determination of five metals in one sample in a wide concentrations range is possible using a low cost apparatus. The profiles of the metal concentrations in interstitial water of subsequent layers of sediments, sampled from Puck Bay, Gdańsk Bay, the Bornholm area and the S?upsk area are presented.     

Voltammetry as an Alternative Tool for Trace Metal Detection in Peloid Marine Sediments

Here was demonstrated for the first time a possible application of abrasive stripping voltammetry in the direct measurement of trace metals in anoxic, sulfidic marine sediments (peloid mud) from a small and shallow (0.2–1 m) marine lagoon in Central Dalmatia, Croatia. Trace amounts of sample compounds are transferred to the graphite electrode surface and electrochemical reduction or oxidation processes are followed by the cyclic voltammetry in seawater or 0.55 M NaCl as electrolyte. After a preelectrolysis at potentials ranging from ?1.0 to ?1.5 V (vs. SCE) a well‐defined anodic stripping peak corresponding to the oxidation of metal deposits generated at deposition potentials is obtained around ?0.74 V (vs. SCE). The same samples were studied by anodic stripping voltammetry at the Hg electrode and inductively coupled plasma‐mass spectrometer (ICP‐MS). ICP‐MS showed higher concentrations of trace metals such as Al, Fe, Mo, Mn. A relatively high concentration of reduced sulfur species (RSS) (10^?3 M) is determined electrochemically in porewater of the peloid mud, indicating that the magnitude of metal enrichment in the sediments is probably controlled by precipitation with sulfide.     

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.     

Stripping Voltammetric Determination of Pb(II) and Cd(II) Based on the Multiwalled Carbon Nanotubes-Nafion-Bismuth Modified Glassy Carbon Electrodes

Abstract

In this work, a new method for the simultaneous determination of Pb(II) and Cd(II) on the multiwalled carbon nanotubes (MWNT)-Nafion-bismuth modified glassy carbon electrode (GCE) using square-wave anodic stripping voltammetry has been studied. Scanning electron microscopy was used to investigate the characteristics of the MWNT-Nafion-bismuth modified GCE. Well-defined sharp stripping peaks were observed in the determination of Pb(II) and Cd(II) simultaneously on this electrode. Under optimized conditions, the lowest detectable concentrations were 50 ng/l for Pb(II) and 80 ng/l for Cd(II) under a 10 min preconcentration. The attractive performances of MWNT-Nafion-bismuth modified GCE demonstrated its application for a simple, rapid, and harmless determination of trace heavy metals.     

Validation of bismuth film electrode for determination of cobalt and cadmium in soil extracts using ICP-MS

A study is presented on the use of the bismuth film electrode (BiFE) operated in the anodic stripping and the cathodic adsorptive stripping voltammetry (ASV, CAdSV) modes, for the determination of two trace heavy metals (Cd and Co, respectively), in soil extract samples. Two types of BiFE were examined in this study: the in situ prepared BiFE, which was employed in ASV determination of Cd, and the ex situ prepared BiFE, which was used in CAdSV of Co with dimethylglyoxime (DMG) as complexing agent. A series of unpretreated soil extracts with varying Cd and Co concentrations were analyzed, and the results obtained compared to those determined using inductively coupled plasma-mass spectrometry (ICP-MS). The results revealed the suitability of stripping analysis at the BiFE for determination of μg l⁻¹ levels of heavy metals in soil extracts. The promising results obtained here, coupled with the non-toxic nature of bismuth (in comparison to commonly used mercury electrodes employed in stripping analysis), offer great promise in centralized and decentralized analysis of trace heavy metals in complex environmental matrices.     

Recent Advances in Anodic Stripping Voltammetry with Bismuth‐Modified Carbon Paste Electrodes

In this article, the results of some recent investigations on two types of bismuth‐modified carbon paste electrodes are presented. In the first study, the bismuth‐film carbon paste electrode (BiF‐CPE) operated in situ and employed in anodic stripping voltammetry of Cd(II) and Pb(II) at the low μg L^?1 level was of interest in view of choosing the proper Bi(III)‐to‐Me(II) concentration ratios (where Me: Pb or Cd). Such optimization has resulted in significant improvement of detection limits down to 1.0 μg L^?1 Cd and 0.8 μg L^?1 for Pb, which allowed us to apply the BiF‐CPE for analysis of selected real samples of tap and sea water. The BiF‐CPE was also further investigated for its application in highly alkaline media. In this case, attention was focused on the complex‐forming capabilities of the OH ^– ions and their effect on the anodic stripping characteristics of some heavy metals (i.e. Cd, Pb, Tl) as well as upon the formation of the bismuth film itself. The last example deals with the continuing characterization of the recently introduced carbon paste electrodes modified with bismuth powder (Bi‐CPEs) which combine the advantageous properties of carbon paste material with the favorable electrochemical properties of bismuth. Three series of electrodes, differing either in the content of metallic bismuth (from 8 to 50% w/w) or in the type of the carbon powder used (two spectroscopic types of graphite and powdered glassy carbon), were compared and the respective relations to the optimal carbon paste composition evaluated. Attractive electroanalytical performance of the Bi‐CPE in anodic stripping voltammetry is demonstrated for selected model mixtures of heavy metals (Mn, Zn, Cd, Pb, Tl, and In).     

A Novel Cell Design for the Improved Stripping Voltammetric Detection of Zn(II), Cd(II), and Pb(II) on Commercial Screen‐Printed Strips by Bismuth Codeposition in Stirred Solutions

A novel electrochemical cell design is proposed to allow fast, reproducible and highly efficient convective transport of dissolved substances to screen‐printed electrochemical three‐electrode strips mounted on miniaturized plastic vessels, with the goal of improving detection limits in disposable electrochemical stripping field sensors. The experimental configuration has been tested for accumulation of the selected heavy metals ions Zn(II), Cd(II), and Pb(II), codeposited with bismuth ions on a carbon disk screen‐printed working electrode before detection by square wave anodic stripping voltammetry. Chemical and instrumental variables of the proposed device and associate electrochemical method were optimized. Selected parameters gave detection limits in the low ng mL^?1 range with moderate deposition time (120 s). Practical applicability was tested on certified water and real samples (tap water and waste water), with acceptable results, suggesting potential usefulness for field environmental monitoring of heavy metals.     

Multivariate analysis of Cd(II), In(III), Tl(I) and Pb(II) in mixtures using square wave anodic stripping voltammetry

Accurate qualitative and quantitative results were obtained by the application of parameter estimation methods, viz. Classical Least Squares ;CLS', Inverse Least Squares ;ILS' and Kalman Filter ;KF' algorithms. These methods were used to separate strongly overlapping electrochemical peaks produced by binary, ternary and quaternary mixtures of traces of cited poisonous heavy metals stripped from the hanging mercury drop electrode in an acetate-bromide electrolyte using the square wave anodic stripping voltammetry. The analysis was achieved using a single standard addition, the concentrations studied were down to 50 nM and molar ratios up to 1:6 for binary mixtures. A statistical analysis of the results was reported. The method was applied for the ultratrace analysis of the cited cations in a sample of sodium hydrogen carbonate AR.     

An optimized digestion method coupled to electrochemical sensor for the determination of Cd, Cu, Pb and Hg in fish by square wave anodic stripping voltammetry

An optimized digestion method coupled to electrochemical detection to monitor lead, copper, cadmium and mercury in fish tissues was developed. Square wave anodic stripping voltammetry (SWASV) coupled to disposable screen-printed electrodes (SPEs) was employed as fast and sensitive electroanalytical method for heavy metals detection. Different approaches in digestion protocols were assessed. The study was focused on Atlantic hake fillets because of their wide diffusion in the human nutrition. Best results were obtained by digesting fish tissue with hydrogen peroxide/hydrochloric acid mixture coupled to solid phase (SP) purification of the digested material. This combined treatment allowed quantitative extraction from fish tissue (muscle) of the target analytes, with fast execution times, high sensitivity and avoiding organic residues eventually affecting electrochemical measurements. Finally, the method has been validated with reference standard materials such as dogfish muscle (DORM-2) and mussel tissues (NIST 2977).