Robotic heavy metal anodic stripping voltammetry: ease and efficacy for trace lead and cadmium electroanalysis

A novel strategy for the automation of trace lead (Pb²⁺) and cadmium (Cd²⁺) anodic stripping voltammetry (ASV) is described. This was achieved using an electrode assembly comprising a small standard reference electrode, a Pt wire counter electrode, and an in situ bismuth-plated pencil lead working electrode for ASV in a robotic device adapted for measurements in a 24-well microtiter plate format. The movement of the electrode assembly through individual wells was by computer-controlled micropositioning, and each microtiter plate run included a sequence of electrode pretreatment, water rinsing, and simultaneous Pb²⁺ and Cd²⁺ ASV measurements. Analyte concentrations down to 2 μg/L (Pb²⁺) and 20 μg/L (Cd²⁺) could be measured in drinking and tap water, a wastewater reference material and a soil sample, with an accuracy and standard deviation typical of stripping analysis. This robotic electrochemical strategy offers automated trace metal analysis with simple instrumentation and is suggested as an option for routine use in analytical laboratories such as those providing environmental heavy metal testing services.     

Selective Determination of Copper (II) Based on Aluminum Silicon Carbide Nanoparticles Modified Glassy Carbon Electrode by Square Wave Stripping Voltammetry

The morphology and structure of as‐prepared aluminum silicon carbide (Al₄SiC₄) were characterized using X‐ray diffraction (XRD) patterns, scanning electron microscope (SEM), transmission electron microscopy (TEM) and UV‐vis spectra. The Al₄SiC₄ nanoparticles modified glassy carbon electrode (GCE) was further investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Based on this, this kind of new electrode was used for the detection of trace Cu²⁺ by square wave anodic stripping voltammetry (SWASV) for the first time. The electrochemical parameters influencing on deposition and stripping of metal ions, such as supporting electrolytes, pH value, deposition potential and deposition time, were also optimized. The results showed that the Al₄SiC₄ modified GCE exhibited excellent stripping response of Cu²⁺ and the stripping peaks response increased linearly with increasing concentration of Cu²⁺ in the ranges of 400 to 2200 nM. Under the optimized conditions the favorable sensitivity of the Al₄SiC₄ modified GCE toward trace Cu²⁺ was 1.49 μA μM⁻¹ and the limit of detection (S/N=3) was estimated to be 2.76 nM. More importantly, Al₄SiC₄ modified GCE had an excellent stability and negligible interference from other coexisting metal ions in the electrochemical determination of Cu²⁺.     

Trace Analysis of Heavy Metals (Cd,Pb, Hg) Using Native and Modified 3D Printed Graphene/Poly(Lactic Acid) Composite Electrodes

Here we investigate the use of 3D printed graphene/poly(lactic acid) (PLA) electrodes for quantifying trace amounts of Hg, Pb, and Cd. We prepared cylindrical electrodes by sealing a 600 μm diameter graphene/PLA filament in a pipette tip filled with epoxy. We characterized the electrodes using scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry in ferrocene methanol. The physical characterization showed a significant amount of disorder in the carbon structure and the electrochemical characterization showed quasi‐reversible behavior without any electrode pretreatment. We then used unmodified graphene/PLA electrode to quantify Hg, and Pb and Cd in 0.01 M HCl and 0.1 M acetate buffer using square wave anodic stripping voltammetry. We were able to quantify Hg with a limit of detection (LOD) of 6.1 nM (1.2 ppb), but Pb and Cd did not present measurable peaks at concentrations below ～400 nM. We improved the LODs for Pb and Cd by depositing Bi microparticles on the graphene/PLA and, after optimization, achieved clear stripping peaks at the 20 nM level for both ions (4.1 and 2.2 ppb for Pb²⁺ and Cd²⁺, respectively). The results obtained for all three metals allowed quantification below the US Environmental Protection Agency action limits in drinking water.     

Selective and Sensitive Determination of Uranyl Ions in Complex Matrices by Ion Imprinted Polymers‐Based Electrochemical Sensor

We report on the design of a UO₂²⁺‐selective electrode based on the use of UO₂²⁺ imprinted polymer nanoparticles (IP‐NPs), and its application for the differential pulse adsorptive cathodic stripping voltammetry determination of uranyl ions. A carbon paste electrode was modified with the IP‐NPs, and differential pulse adsorptive cathodic stripping voltammetry was applied as the detection technique after open‐circuit sorption of UO₂²⁺ ions. The modified electrode responses to UO₂²⁺ was linear in the 0.1 µg L^?1 to 10 µg L^?1 and in the 0.01 mg L^?1 to 10 mg L^?1. The method detection limit of the sensor was 0.03 µg L^?1.     

Fabrication and Characterization of Carbon Nanotube‐Hydroxyapatite Nanocomposite: Application to Anodic Stripping Voltammetric Determination of Cadmium

A novel chemically modified electrode for stripping determination of cadmium is presented in this paper, based on carbon nanotube‐hydroxyapatite (CNT‐HAP) nanocomposite, which can be prepared by an easy and effective one‐step sonication. The newly synthesized nanocomposite was characterized with FTIR, TEM, and electrochemical methods. Due to the combination of the strong absorption ability of HAP and excellent electroanalytical properties of CNTs, the GC/CNT‐HAP electrode has been successfully used for determination of Cd²⁺ by anodic stripping voltammetry with a linear range of 20 nM–3 μM. The sensitivity and detection limit are 25.6 μA/μM and 4 nM, respectively. The practical application of the proposed electrode has been carried out for the determination of trace levels of Cd²⁺ in real water samples.     

Simultaneous Adsorptive Cathodic Stripping Voltammetric Determination of Nickel(II) and Cobalt(II) at an In Situ Bismuth‐Modified Gold Electrode

A study on the simultaneous determination of Ni(II) and Co(II) dimethylglyoximates (Ni‐DMG and Co‐DMG) through adsorptive cathodic stripping voltammetry at an in situ bismuth‐modified gold electrode (Bi‐AuE) is reported. The key operational parameters, such as Bi(III) concentration, accumulation potential and accumulation time were optimized and the morphology of the Bi‐microcrystals deposited on the Au‐electrode was studied. The Bi‐AuE allowed convenient analysis of trace concentrations of solely Ni(II) or of Ni(II) and Co(II) together, with cathodic stripping voltammograms characterized by well‐separated stripping peaks. The calculated limit of detection (LOD) was 40 ng L^?1 for Ni(II) alone, whereas the LOD was 98 ng L^?1 for Ni(II) and 58 ng L^?1 for Co(II), when both metal ions were measured together. The optimized method was finally applied to the analysis of certified spring water (NIST1640a) and of natural water sampled in the Lagoon of Venice. The results obtained with the Bi‐AuE were in satisfactory agreement with the certified values and with those provided by complementary techniques, i.e., ICP‐OES and ICP‐MS.     

Sensitive Detection of Capsaicin by Adsorptive Stripping Voltammetry at a Boron‐Doped Diamond Electrode in the Presence of Sodium Dodecylsulfate

In the present paper, a sensitive electroanalytical methodology for the determination of capsaicin using adsorptive stripping voltammetry (AdSV) at a boron‐doped diamond (BDD) electrode is presented. The voltammetric results indicate that in the presence of sodium dodecylsulfate (SDS) the BDD electrode remarkably enhances the oxidation of capsaicin which leads to an improvement of the peak current with a shift of the peak potential to less negative values. A linear working range of 0.05 to 6.0 µg mL^?1 (0.16–20 µM) with a detection limit of 0.012 µg mL^?1 (0.034 µM) has been obtained using BDD electrode by AdSV.     

Ordered Mesoporous Carbon and Thiolated Polyaniline Modified Electrode for Simultaneous Determination of Cadmium(II) and Lead(II) by Anodic Stripping Voltammetry

The fabrication and evaluation of a glassy carbon electrode (GCE) modified with ordered mesoporous carbon (OMC), 2‐mercaptoethanesulfonate (MES)‐tethered polyaniline (PANI) and bismuth for simultaneous determination of trace Cd²⁺ and Pb²⁺ by differential pulse anodic stripping voltammetry (DPASV) are presented here. The morphology and electrochemical properties of the fabricated electrode were respectively characterized by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Experimental parameters such as PANI disposition, preconcentration potential, preconcentration time and bismuth concentration were optimized. Under optimum conditions, the fabricated electrode exhibited linear calibration curves ranged from 1 to 120 nM for Cd²⁺ and Pb²⁺. The limits of detection (LOD) were 0.26 nM for Cd²⁺ and 0.16 nM for Pb²⁺ (S/N=3), respectively. Additionally, repeatability, reproducibility, interference and application were also investigated, and the proposed electrode exhibited excellent performance. The proposed method could be extended for the development of other new sensors for heavy metal determination.     

Application of Novel Zn‐Ferrite Modified Glassy Carbon Paste Electrode as a Sensor for Determination of Cd(II) in Waste Water

This paper describes the preparation of a new sensor based on Zn‐ferrite modified glassy carbon paste electrode and its electrochemical application for the determination of trace Cd(II) ions in waste waters using differential pulse anodic stripping voltammetry (DPASV). Different Zn/Ni ferrite nanoparticles were synthesized and characterized using scanning electron microscopy (SEM) and X‐ray powder diffraction (XRPD). The prepared ferrite nanoparticles were used for the preparation of Zn‐ferrite‐modified glassy carbon paste electrode (ZnMGCPE) for determination of Cd(II) at nanomolar levels in waste water at pH 5. The different parameters such as conditions of preparation, Zn²⁺/Ni²⁺/Fe²⁺ ratio and electrochemical parameters, percentage of modifier, accumulation time, pH and accumulation potential were investigated. Besides, interference measurements were also evaluated under optimized parameters. The best voltammetric response was observed for ZnFe₂O₄ modifier, when the percentage of modifier was 3 %, accumulation time 9 min, pH of supporting electrolyte 5 and accumulation potential ?1.05 V. Thus prepared electrode displays excellent response to Cd(II) with a detection limit of 0.38 ppb, and selective detection toward Cd(II) was achieved.     

Non-conductive nanomaterial enhanced electrochemical response in stripping voltammetry: The use of nanostructured magnesium silicate hollow spheres for heavy metal ions detection

Nanostructured magnesium silicate hollow spheres, one kind of non-conductive nanomaterials, were used in heavy metal ions (HMIs) detection with enhanced performance for the first time. The detailed study of the enhancing electrochemical response in stripping voltammetry for simultaneous detection of ultratrace Cd²⁺, Pb²⁺, Cu²⁺ and Hg²⁺ was described. Electrochemical properties of modified electrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The operational parameters which have influence on the deposition and stripping of metal ions, such as supporting electrolytes, pH value, and deposition time were carefully studied. The anodic stripping voltammetric performance toward HMIs was evaluated using square wave anodic stripping voltammetry (SWASV) analysis. The detection limits achieved (0.186 nM, 0.247 nM, 0.169 nM and 0.375 nM for Cd²⁺, Pb²⁺, Cu²⁺ and Hg²⁺) are much lower than the guideline values in drinking water given by the World Health Organization (WHO). In addition, the interference and stability of the modified electrode were also investigated under the optimized conditions. An interesting phenomenon of mutual interference between different metal ions was observed. Most importantly, the sensitivity of Pb²⁺ increased in the presence of certain concentrations of other metal ions, such as Cd²⁺, Cu²⁺ and Hg²⁺ both individually and simultaneously. The proposed electrochemical sensing method is thus expected to open new opportunities to broaden the use of SWASV in analysis for detecting HMIs in the environment.     

Enhanced Specificity and Sensitivity for the Determination of Nickel(II) by Square-wave Adsorptive Cathodic Stripping Voltammetry at Disposable Graphene-modified Pencil Graphite Electrodes

Chemical sensors relying on graphene-based materials have been widely used for electrochemical determination of metal ions and have demonstrated excellent signal amplification. This study reports an electrochemically reduced graphene oxide (ERGO)/mercury film (HgF) nanocomposite-modified pencil graphite electrode (PGE) prepared through successive electrochemical reduction of graphene oxide (GO) sheets and an in situ plated HgF. The ERGO-PG-HgFE, in combination with dimethylglyoxime (DMG) and square-wave adsorptive cathodic stripping voltammetry (SW-AdCSV), was evaluated for the determination of Ni²⁺ in tap and natural river water samples. A single-step electrode pre-concentration approach was employed for the in situ Hg-film electroplating, metal-chelate complex formation, and non-electrolytic adsorption at –0.7 V. The current response due to nickel-dimethylglyoxime [Ni(II)-DMG₂] complex reduction was studied as a function of experimental paratmeters including the accumulation potential, accumulation time, rotation speed, frequency and amplitude, and carefully optimized for the determination of Ni²⁺ at low concentration levels (μg?L^?1) in pH 9.4 of 0.1 M NH₃–NH₄Cl buffer. The reduction peak currents were linear with the Ni²⁺ concentration between 2 and 16?μg?L^?1. The limits of detection and quantitation were 0.120?±?0.002?µg?L^?1 and 0.401?±?0.007?µg?L^?1 respectively, for the determination of Ni²⁺ at an accumulation time of 120?s. The ERGO-PG-HgFE further demonstrated a highly selective stripping response toward Ni²⁺ determination compared to Co²⁺. The electrode was found to be sufficiently sensitive to determine metal ions in water samples at 0.1?µg?L^?1, well below the World Health Organization standards.     

Cathodic Adsorptive Stripping Voltammetric Determination of the Antitumor Drug Rutin in Pharmaceuticals, Human Urine, and Blood Serum

Cathodic adsorptive stripping voltammetry (CASV) was applied for the determination of rutin in pharmaceuticals, human urine, and blood serum. An electrochemical stripping procedure for trace measurements of rutin was developed based on the adsorption of the Cu²⁺-rutin complex on a hanging mercury drop electrode and applied to the quantification of the drug. Cyclic voltammetry was used to characterize the interfacial and redox behavior of the adsorbed Cu²⁺-rutin complex. Experimental and instrumental parameters for quantitative determination were optimized, and a detection limit of 4.9 × 10⁻⁹ mol · L⁻¹ in presence of Cu²⁺-ions for quantification of rutin under optimum conditions was derived. The sharp peak of the adsorbed Cu²⁺-rutin complex associated with an effective interfacial accumulation of this compound facilitates the determination of rutin in biological fluids with good recoveries. The degree of interference from potentially present metal ions and organic compounds on the CASV signal for Cu²⁺-rutin complex was evaluated.     

The determination of molybdenum in selected mushrooms by stripping voltammetry

The highly sensitive method of adsorptive stripping voltammetry (AdSV), with differential pulse steps, was performed at a mercury film electrode and has been applied here for the determination of trace molybdenum content in selected wild mushrooms. Fruiting body caps of 12 selected macrofungi species from Basidiomycetes have been investigated. Molybdenum content of investigated samples was determined in the range of 0.006 to 0.38 mg kg⁻¹ of dry matter. The highest value of molybdenum content was found in Leccinum rufum and the lowest in Lactarius deliciosus.     

Electrochemical Detection of Lead Ion Based on a Peptide Modified Electrode

A novel biosensor harnessing a peptide layer which has specific affinity to lead ion proved to be highly effective for electrochemical analysis of lead ions. The peptide modified electrode was used for the electrochemical analysis of various trace metal ions by square wave voltammetry. Compared to the other ions investigated, the peptide modified electrode was found to be highly selective to Pb²⁺ in the range of 50–700 nM. Furthermore, the biosensor exhibited a high reusability and good spike recovery in the tap water containing various concentration of Pb²⁺.     

Square Wave‐Anodic Stripping Voltammetric Determination of Copper at a Bismuth Film/Glassy Carbon Electrode Using 3‐[(2‐Mercapto‐Vinyl)‐Hydrazono]‐ 1,3‐Dihydro‐Indol‐2‐One

This study reports a highly sensitive electrochemical sensor based on Bi film modified glassy carbon electrode (BiF/GCE) for total determination and speciation trace concentrations of copper(II) ions in environmental water samples. Square wave‐adsorptive anodic stripping voltammetric (SW‐ASV) experiment was performed for monitoring selective accumulation of copper(II) with reagent 3‐[(2‐mercapto‐vinyl)‐hydrazono]‐1,3‐dihydro‐indol‐2‐one (MHDI) at pH 9–10. The mechanism of the electrode reaction of Cu²⁺‐MHDI complex was safely assigned. The sensor exhibited a wide linear range (3.22×10⁻⁹–2.0×10⁻⁷ mol L⁻¹) with lower limits of detection (LOD) and quantitation (LOQ) of 9.6×1⁻¹⁰ and 3.22×10⁻⁹ mol L⁻¹, respectively (R²=0.9993). The proposed sensor exhibited interference from active metal ions e. g. Cd, Hg. The performance of the proposed method was compared successfully with most of the reported methods and comparable efficiencies were obtained. The analytical utility of the proposed SW‐ASV method has been successfully validated for trace analysis of copper(II) in environmental water samples. The method offers a precise, accurate approach with good reproducibility, robustness, ruggedness, and cost effectiveness.     

On-line stripping voltammetry of trace metals at a flow-through bismuth-film electrode by means of a hybrid flow-injection/sequential-injection system

In this work, we describe an automated stripping analyzer operating on a hybrid flow-injection/sequential-injection (FIA/SIA) mode and utilizing a bismuth-film electrode (BiFE) as a flow-through sensor for on-line stripping voltammetry of trace metals. The instrument combines the advantages of FIA and SIA and is characterised by simplicity, low-cost, rapidity, versatility and low consumption of solutions. The proposed analytical flow methodology was applied to the determination of Cd(II) and Pb(II) by anodic stripping voltammetry (ASV) and of Ni(II) and Co(II) by adsorptive stripping voltammetry (AdSV). The steps of the rather complex experimental sequence (i.e. the bismuth-film formation, the analyte accumulation, the voltammetric stripping and the electrode cleaning/regeneration) were conducted on-line and the critical parameters related to the respective analytical procedures were investigated. In ASV, for a accumulation time of 180 s the limits of detection for Cd(II) and Pb(II) were 2 and 1 μg l⁻¹, respectively (S/N = 3) and the relative standard deviations were 5.3% and 4.7%, respectively (n = 8). In AdSV, for a total sample volume of 1000 μl, the limits of detection for Ni(II) and Co(II) were 1 μg l⁻¹ (S/N = 3) and the relative standard deviations were 5.5% and 6.2%, respectively (n = 8). The measurement frequency ranged between 15 and 20 stripping cycles h⁻¹. The results indicate that the BiFE is well suited as a flow-through detector for on-line stripping analysis and, by virtue of its low toxicity, can serve as a viable alternative to mercury-based flow-through electrodes.     

Novel disposable microfabricated antimony-film electrodes for adsorptive stripping analysis of trace Ni(II)

This work describes a novel type of antimony electrode for adsorptive stripping voltammetry (AdSV). The electrode was microfabricated by coating a silicon chip with a thin antimony-film by means of sputtering and the active area of the electrode was defined by photolithography. The resulting antimony-film electrodes (SbFEs) were characterized by optical and electrochemical techniques. The sensors were tested for the detection of low concentrations of Ni(II) by AdSV in the presence of dimethylglyoxime. Well-formed stripping peaks and a linear dependence of the stripping peak current on the Ni(II) concentration were observed on the microfabricated SbFEs while comparative measurements attempted with electroplated SbFEs were unsuccessful. Utilizing thin-film technology for the formation of the antimony-film extends the scope of these devices as mercury-free sensors in AdSV.     

Remote Stripping Analysis of Lead and Copper by a Mercury‐Coated Platinum Microelectrode

The performance of a remote stripping sensor based on mercury microelectrodes (MM‐RS) for the in situ detection of trace metals in aquatic systems, was investigated. The submersible device employed here consists of a single mercury‐coated platinum disk microelectrode assembled in a two‐electrode cell configuration, and connected remotely by a 30 m long shielded cable. First, the MM‐RS device is characterized in Ru(NH₃) and Pb²⁺ synthetic aqueous solutions by applying cyclic voltammetry and anodic stripping voltammetry (ASV), respectively. The results obtained show that the small electrode dimensions and the related low currents involved, the long remote connection cable or the use of a two‐electrode system do not cause noise effects or uncompensated resistance problems in the measurements. Using square‐wave voltammetry in the stripping step, linear calibration graphs for Pb²⁺ ions over the concentration range 1×10^?9?5×10^?7 M were obtained, and a detection limit, DL, of 0.15 nM was found. The relative standard deviation (RSD), at 5×10^?8 M Pb²⁺ level, was within 5%. The effect of humic acid and of sodium dodecylsulfate surfactants on the stripping responses was also investigated. The performance of the submersible MM‐RS system was tested for the in situ monitoring of the labile fraction of lead and copper on a site of the Lagoon of Venice. In situ Pb²⁺ and Cu²⁺ concentrations were monitored for about 8 hours, by leaving the sensor immersed in the lagoon waters (2 m depth) and recording the response every hour. Under these field conditions, reliable in situ data for the labile fraction of these metal ions with a satisfactory precision, the RSD being within 7 and 9 % for lead and copper, respectively, were obtained.     

Simultaneous Detection of Heavy Metals by Anodic Stripping Voltammetry Using Carbon Nanotube Thread

Carbon nanotube (CNT) threads are a type of CNT arrays that consist of super long CNTs. CNT threads inherit the advantages of CNTs, while avoiding the potential toxicity caused by individual CNTs. Electrodes based on CNT threads were fabricated and used for simultaneous detection of trace levels of Cu²⁺, Pb²⁺ Cd²⁺ and Zn²⁺ by anodic stripping voltammetry (ASV). The detection limits are 0.27 nM, 1.5 nM, 1.9 nM and 1.4 nM for Cu^2+, Pb²⁺, Cd²⁺ and Zn²⁺, respectively, in 0.1 M acetate buffer pH 4.5. The CNT thread electrode gives well‐defined, reproducible and sharp stripping signals for individual and simultaneous detection of heavy metals.     

Electroanalysis of the Anthelmintic Drug Bithionol at Edge Plane Pyrolytic Graphite Electrode

An electrochemical study of the anthelmintic drug bithionol using edge plane pyrolytic graphite electrode (EPPGE) is presented for the first time by applying different electrochemical techniques, such as cyclic voltammetry (CV), square‐wave voltammetry (SWV), square‐wave adsorptive stripping voltammetry (SWAdSV), and alternating current (AC) impedance spectroscopy. Mechanistic aspects of the electrode reaction were studied implying a quasireversible electrode reaction from an adsorbed state of the reactant, coupled with a follow‐up chemical reaction to a final electroinactive product. The overall mechanism appears totally irreversible under conditions of CV at moderate scan rate, while being quasireversible under conditions of the fast SWV. Furthermore, an optimisation of the analytical procedure for quantitative determination of bithionol was conducted by applying SWV in an adsorptive stripping mode. The calibration curve was constructed in the concentration range of 0.1–1.0 μmol L^?1 (R²=0.9984) with a sensitivity of 3.6 μA L μmol^?1 and LOD of 26.7 nmol L^?1. The simple and sensitive SWAdSV procedure was proved to be suitable for the analysis of spiked urine samples.