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.     

Amperometric biosensor based on denatured DNA for the study of heavy metals complexing with DNA and their determination in biological, water and food samples

Amperometric biosensor (BS) has been elaborated based on the stationary mercury-film electrode (SMFE) with silver support and cellulose nitrate (CN) membrane containing immobilized single-stranded DNA (ssIDNA). The sorption isotherms and ssDNA-heavy metal binding constants have been obtained with the BS. According to these data, the chosen heavy metals form the following series of binding strength with ssIDNA: Pb(II)>Fe(III)>Cd(II). It has been found that upon the competitive adsorption, there exists practically simultaneous sorption of different ions at ssIDNA containing membrane. The method of the determination of heavy metals based on preconcentration of metal ions on the BS followed by the destruction of DNA-metal complexes with ethylenediamine tetraacetate (EDTA) and voltammogram recording has been proposed. The lower limits of detectable contents are 1.0x10(-10), 1.0x10(-9) and 1.0x10(-7) mol l(-1) for Pb(II), Cd(II) and Fe(III), respectively. Heavy metals have been assayed in natural and drinking water, milk and blood serum samples even under simultaneous presence with a selectivity factor of 1:10. The effect of matrix components has been estimated.     

Multicomponent Analysis of Liquids by Test Methods

Test strips were proposed for the simultaneous determination of the sum of heavy metals, iron(III), copper, zinc, total alkalinity, hardness, chlorides, sulfates, nitrates, nitrites, and fluorides, and composite test strips were proposed for the determination of copper, iron(III), and cobalt. Determination is based on the dependence of the length of colored zones of indicator papers sealed in a polymer film and with one edge in contact with the test solution on the concentrations of the analytes. The analytical range is 0.1–1000 mg/L. Procedures were developed for the determination of the above components in blood serum, hair, and solutions. The relative standard deviation is no higher than 40%, and the time of analysis is 15–20 min. Two-layer and composite test plates were proposed for the simultaneous determination of mercury(II), copper, iron(III), zinc, cadmium, fluorides, and chlorides by the diameter of colored zones after the impregnation of plates with the test liquid through a hole in the film with which the indicator paper was sealed. Two-layer test plates are squares of indicator paper, which do not contact with each other and are sealed with three layers of a transparent polymer film. Composite test plates are 3 × 3-cm squares made of indicator paper triangles and sealed with a polymer film from the two sides. Analytical ranges of different components are 0.5–50 mg/L. Procedures were developed for the determination of the above elements in galvanic slimes. The relative standard deviation is no higher than 40%; the time of analysis is 2–5 min.     

Simultaneous determination of copper, mercury and zinc in water with a tailored fluorescent bipyridine ligand entrapped in silica sol-gel

A novel fluorescent ligand, (4-[(E)-2-(4'-methyl-2,2'-bipyridin-4-yl)vinyl]phenol) (abbreviated BSOH), has been designed and prepared for simultaneous determination of heavy metals in water. Its photophysical and photochemical properties in the absence and in the presence of Cd(II), Cu(II), Hg(II), Ni(II) and Zn(II) were determined, and the respective complexation constants (7.4 × 10(3)-2.8 × 10(8) l mol(-1)) and stoichiometries were extracted thereof. The Stern-Volmer emission intensity and lifetime plots indicate an efficient static quenching of the indicator dye with the heavy metals. The BSOH fluorescent reagent has been successfully immobilised in a silica sol-gel matrix for automation of the analytical method, and the sensing phase demonstrated a reversible response to Cu(II), Hg(II) and Zn(II) but not to Cd(II) and Ni(II). Characterisation of the sensor showed that its response to those heavy metals is linear in the 2.5 to 50 μmol l(-1) range, with a response time (t (90)) on the order of 100 min, providing detection limits of 9.0 × 10(-7), 4.7 × 10(-7) and 2.9 × 10(-7) mol l (-1) for Zn(II), Cu(II) and Hg(II), respectively. Due to the stability of the immobilised ligand, which presented no leaching from the sol-gel matrix, the simultaneous determination of the three cations in water was feasible by employing multivariate calibration techniques coupled to fluorescence quenching measurements. The sensor was validated with recovery tests by addition of Cu(II) and Hg(II) ions to spring waters, providing results with standard errors lower than 4.1 μmol l (-1).     

Amperometric detection of unithiol complexes of heavy metals in high-performance liquid chromatography

It was demonstrated that Pb(II), Cd(II), Hg(II), Ni(II), Co(II), and Cu(II) can be indirectly determined as their unithiol complexes by amperometric detection under static and HPLC conditions. Factors affecting the Chromatographic separation and amperometric detection of metal complexes of unithiol were studied. Two designs of flow electrochemical cells (thin-layer and wall-jet cells) and three electrode materials (platinum, graphite, and glassy carbon) were compared. The best sensitivity was attained for an amperometric detector with wall-jet flow cell and a graphite indicator electrode. The detection limits for Hg(II), Pb(II), and Cd(II) were 0.9, 0.3, and 0.1 μg/mL, respectively. The Chromatographic determination of heavy metals in a sample of waste water was carried out using the amperometric detector     

Date pits waste as a solid phase extraction sorbent for the analysis of lead in wastewater and for use in manufacturing brick: An eco-friendly waste management approach

Lead (Pb(II)), an extremely hazardous heavy metal that has been shown to have detrimental effects on both the environment and humans, mostly gets into the ecosystem through industrial activities. In this work, a new solid-phase extraction (SPE) based on treated date pits bio-sorbent and iCAP Q inductively-coupled plasma mass spectrometry (iCAP Q ICP/MS) method has been optimized for the trace determination of Pb(II) in various industrial wastewater effluents. A cost-effective biomass material was prepared from date pits (DP), and chemically modified with H₂O₂ and successively used as SPE bio-sorbent for Pb(II) extraction. Extracting solutions for instance H₂SO₄, HNO₃ and HCl at various concentrations (1–5 mM) were optimized, and best extraction of Pb(II) was obtained by HCl (1 mM). The optimized SPE and iCAP Q ICP/MS method has offered excellent validation conditions in terms of coefficient of determination (CoD, R² > 0.999), detection limit (DL, 0.011 µg/L), quantification limit (QL, 0.034 µg/L), and run-to-run and day-to-day precision (RSD < 6 %). The optimized procedure was practically applied in the determination of Pb(II) in industrial wastewater comprising iron and steel, textile, printing and battery industries. Among the analyzed samples, the battery industry produced higher amounts of Pb(II) (18.55 µg/L) followed by iron and steel (14.65 µg/L), petroleum (12.38 µg/L) printing (5.78 µg/L) and textile (3.76 µg/L) industries. The recovery values were achieved between 95 % and 99 %. The obtained results have established the appropriateness of the offered technique as a new useful method for the routine examination of Pb(II) in industrial wastes. In addition, the current method could be expansively used in the proficient removal and identification of other heavy metals contaminants from similar matrices. Further, the metal ions saturated bio-sorbents were used in the preparations of bricks and it was found to be a successful approach for heavy metals and agricultural waste management.     

Preparation and properties of a new chelating resin containing imidazolyl azo groups

 A new chelating resin incorporating imidazolyl azo groups into a matrix of polystyrene divinylbenzene has been prepared. The exchange capacity of the resin for the ions mercury(II), silver(I) and lead(II) as a function of pH has been determined. The resin exhibits no affinity to alkali, or alkaline earth metals. It is highly selective for only mercury(II) and silver(I). In column operation it has been observed that mercury(II) in trace quantities is very effectively removed from river water spiked with mercury(II) at the usual pH of natural waters. Received: 2 January 1996/Revised: 11 April 1996/Accepted: 16 April 1996     

Simultaneous determination of traces of heavy metals by solid-phase spectrophotometry

A coupling sensitive solid phase spectrophotometric (SPS) procedure for determination of traces of heavy metals (Me-SPS) and multicomponent analysis by multiple linear regressions (MA), a simple methodology for simultaneous determination of metals in mixtures was inaugurated. The Me-SPS procedure is based on sorption of heavy metals on PAN-resin and direct absorbance measurements of colour product Me-PAN sorbed on a solid carrier in a 1-mm cell. This methodology (Me-SPS-MA) was checked by simultaneous determination of metals in synthetic mixtures with different compositions and contents of metals important in pharmaceutical practice: Zn, Pb, Cd, Cu, Co, and Ni. Good agreement between experimental and theoretical amounts of heavy metals is obtained from the recovery test (78.3–110.0%). The proposed method enables determination of particular metal ion at the ng mL⁻¹ level and it was successfully applied to the determination impurities from heavy metal traces in pharmaceutical substances (Cu in ascorbic acid, Pb in glucose, and Zn in insulin). The proposed procedure could be possible contribution to the development of pharmacopoeial methodology for a heavy metals test.     

Cathodic stripping voltammetric determination of selenium(IV) at a thin-film mercury electrode in a thiocyanate-containing electrolyte

The well-known method for the determination of selenium(IV), which is based on the cathodic stripping voltammetry of copper(I) selenide, has been adapted for application at the thin-film mercury electrode on glassy carbon (TFME). Insufficient reproducibility and sensitivity have been overcome by using a 0.1 mol/L HClO₄ electrolyte solution containing 0.02 mol/L thiocyanate ions. Thiocyanate ions have been found to increase the peak height of the selenium response and shift it to more positive potentials. This behaviour is explained by an adsorption of SCN^– at the interface glassy carbon/Cu₂Se and its action as an electron transfer catalyst between glassy carbon and copper(I) selenide. A 3σ-detection limit of 75 ng/L Se^(IV) has been achieved. The relative standard deviation is 5.2% at 5 μg/L selenium(IV). The influence of cadmium(II), arsenic(III), zinc(II), iron(III) and lead(II) ions on the selenium response has been studied. In case of lead ions, a new signal occurred at more negative potentials than the reduction of Cu₂Se. This signal, which is probably due to the reduction of PbSe, can also be used for the determination of selenium(IV). Received: 13 November 1996 / Revised: 19 December 1996 / Accepted: 24 December 1996     

New test tools for determination of trace metals using polydentate cellulose

New test tools have been developed for the rapid determination of trace metals: Ag, Cd, Co, Cu(II), Fe(II,III), Hg(II), Pd and Zn, using polydentate irregular α-celluloses, containing in the 6 position the fragments heterylformazane or heterylhydrazone, with a pocket device for preconcentration. Received: 17 June 1997 / Revised: 1 November 1997 / Accepted: 6 November 1997     

Adsorption of Cu(II), Zn(II), Ni(II), Pb(II), and Cd(II) from aqueous solution on Amberlite IR-120 synthetic resin

The adsorption of copper(II), zinc(II), nickel(II), lead(II), and cadmium(II) on Amberlite IR-120 synthetic sulfonated resin has been studied at different pH and temperatures by batch process. The effects of parameters such as amount of resin, resin contact time, pH, and temperature on the ion exchange separation have been investigated. For the determination of the adsorption behavior of the resin, the adsorption isotherms of metal ions have also been studied. The concentrations of metal ions have been measured by batch techniques and with AAS analysis. Adsorption analysis results obtained at various concentrations showed that the adsorption pattern on the resin followed Freundlich isotherms. Here we report the method that is applied for the sorption/separation of some toxic metals from their solutions.     

New test tools for determination of trace metals using polydentate cellulose

New test tools have been developed for the rapid determination of trace metals: Ag, Cd, Co, Cu(II), Fe(II,III), Hg(II), Pd and Zn, using polydentate irregular α-celluloses, containing in the 6 position the fragments heterylformazane or heterylhydrazone, with a pocket device for preconcentration. Received: 17 June 1997 / Revised: 1 November 1997 / Accepted: 6 November 1997     

Pyrimidinethiol as a reagent for extraction separation of platinum metals and gold Determination of Pd(II), Os(VIII) and Ru(III)

The solvent extraction separation of Pt(IV), Pd(II), Os(VIII), Ru(III) and Au(III) from one another and also from Rh(III) and Ir(III) with 1-(2'-nitro-4'-tolyl)-4,4,6-trimethyl-(1H, 4H)-2-pyrimidinethiol has been investigated. Photometric procedures have been developed for the determination of Pd(II), Os(VIII) and Ru(III) with the same reagent. The reagent allows the enrichment of Pd(II) and Au(III) at the trace level from a large volume of aqueous medium even in the presence of base metals. The method can be used for the determination of platinum metals and gold in alloys.     

Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination

The selective determination of metals in waste solutions is a very important aspect of the industry and environmental protection. Knowledge of the contents and composition of the waste can contribute to design an efficient process separation and recovery of valuable metals. The problematic issue is primarily the correct determination of metals with similar properties such as palladium and platinum. Thus this paper focuses on the development of a selective method that enables Pd(II) determination in the presence of Pt(IV) ions using the azo-dye tropaeolin OO (TR). For this purpose, the process of the metalorganic complex formation and Pd(II) ions determination were studied by using UV–Vis spectrophotometry under different conditions: solvents (water and B-R buffer), pH (2.09–6.09), temperature (20–60 °C), anions and cations concentrations. The formed metalorganic complex between Pd and tropaeolin OO allows for distinguishing Pd(II) ions from both platinum complexes, i.e. Pt(II), Pt(IV). Moreover, the proposed method can be applied to solutions containing both chloride and chlorate ions. The obtained characteristic spectrum with two maxima allows the determination of palladium even in the presence of other cations (Na, K, Mg, Zn, Co, Ni, Al) and changed concentrations of Pt(IV) ions. Furthermore, the developed spectrophotometric method for the Pd(II) ions determination using tropaeolin OO is characterized by high selectivity towards palladium ions.     

Stripping analysis of heavy metals in tap water using the bismuth film electrode

A commercially available screen-printed carbon electrode coated with an ex situ deposited bismuth film (BiSPCE) has been applied to the determination of Pb(II) and Zn(II) ions in tap water (Barcelona water distribution network) by means of stripping voltammetry (SV) and stripping chronopotentiometry (SCP). A good reproducibility of the measurements and a satisfactory agreement between SV and SCP data were observed for both heavy metal ions. Although, in principle, the procedure could be also suited to the determination of Cd(II), this species was not detected. The results were also consistent with the routine ICP-OES measurements of the water distribution company, thus confirming the potential usefulness of such BiSPCE disposable devices for the analysis of heavy metals in natural waters.      

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.     

Microdetermination of Heavy Metal Chelates by High-Performance Liquid Chromatography

Abstract

Adsorption chromatography of diethyldithiocarbamate chelates of heavy metals is described. Determination of heavy metals including Hg (II), Cd (II), Pb (II), Cr (VI), Bi (III) and Cu (II) in micro to nano gram order is successfully carried out with good accuracy and reproducibility by a deactivated silica gel column. Separative microdetermination of these chelates is accomplished within 12 min, and selective determination is also possible by choosing the detection wavelength of a UV detector.     

Graphene Oxide‐Modified Electrode Coated with in‐situ Antimony Film for the Simultaneous Determination of Heavy Metals by Sequential Injection‐Anodic Stripping Voltammetry

The proposed chemically modified electrode was graphene oxide that was synthesized via Hummer's method followed by reduction of antimony film by in‐situ electrodeposition. The experimental process could be concluded in three main steps: preparation of antimony film, reduction of analyte ions on the electrode surface and stripping step under the conditions of square wave anodic stripping voltammetry (SWASV). A simple and rapid approach was developed for the determination of heavy metals simultaneously based on a sequential injection (SI), an automated flow‐based system, coupled with voltammetric method using antimony‐graphene oxide modified screen‐printed carbon electrode (SbF‐GO‐SPCE). The effects of main parameters involved with graphene oxide, antimony and measurement parameters were also investigated. Using SI‐SWASV under the optimal conditions, the proposed electrode platform has exhibited linear range from 0.1 to 1.5 M. Calculated limits of detection were 0.054, 0.026, 0.060, and 0.066 μM for Cd(II), Pb(II), Cu(II) and Hg(II), respectively. In addition, the optimized method has been successfully applied to determine heavy metals in real water samples with acceptable accuracy of 94.29 – 113.42 % recovery.     

Voltammetric Analysis of Trace Levels of Platinum Group Metals – Principles and Applications

The compelling use of autocatalytic converters, containing platinum group metals (PGMs), has been the cause, in the environmental and biological matrices, of an increasing concentration of such metals. For this reason, in the last decade, the literature has reported several papers regarding analytical procedures for the determination of Pt(II), Pd(II) and Rh(III) in real samples, generally employing spectroscopic methods. The present review intends to highlight the contribution of the voltammetric techniques for the determination of these metals, including also those less investigated, i.e. Iridium, Osmium and Ruthenium.