Determination of Ultratrace Thallium(I) by Anodic Stripping Voltammetry at Bismuth Film Electrodes Following Double Deposition and Stripping Steps

The double deposition and stripping steps were proposed to increase the sensitivity in anodic stripping voltammetry of thallium(I). Two in situ plated bismuth film electrodes with drastically different surface areas were exploited for the measurements. Thallium was at first deposited at the electrode with a large surface area. As the deposition step at the large electrode was finished, the electrode was moved at a short distance to the small one. The thallium stripped from the large electrode was then accumulated at the second electrode. Taking into account the small volume of space between the electrodes, the concentration of Tl(I) between the electrodes was drastically higher than that in the bulk solution. The deposition step at the second electrode was performed from solution with a higher concentration of Tl(I) therefore the detection limit was lowered. The calibration graph was linear from 5×10^?11 to 5×10^?9 mol L^?1 following deposition time of 300 s at the first and the second electrode.     

Sensitive Anodic Stripping Voltammetric Copper Ions Determination Performed in Double Deposition and Double Stripping Steps System for Real Water Samples Analysis

The article reports on utilization of double deposition and stripping steps for increasing sensitivity of Cu(II) determination by anodic stripping voltammetry (ASV) at two lead film working electrodes. A significant preconcentration of copper was achieved thanks to utilization of a simple design of four electrodes system that gives possibility to perform one measurement cycle consisting of two deposition and two stripping steps. Due to the fact that deposition step is doubled, the concentration of Pb(II) needed to lead film electrodes formation was significantly reduced as compared to traditional procedures using three electrodes system. The analytical procedure of Cu(II) determination was optimized. The experimental factors: supporting electrolyte's pH and its concentration, lead ions concentration, potential and time of deposition at both working electrodes were studied. The Cu(II) peak current was linearly dependent on its concentration from 5×10^?10 to 2×10^?8 mol L^?1 (deposition time of 270 and 160 s at the first and the second working electrode, respectively). The obtained detection limit for copper ions determination was 2.1×10^?10 mol L^?1. The described procedure was validated by analysis of two water certified reference materials. The described procedure was also utilized for real water sample analysis.     

溶出伏安法同时测定矿山地下水中痕量砷铅

本文以电化学预处理的金电极为工作电极,采用线性扫描溶出伏安法实现了矿山地下水中痕量As3+、Pb2+的同时测定。研究了金电极的预处理方法、不同预富集时间和不同电解质对重金属离子测定的影响规律。研究发现,电化学预处理有利于金电极对重金属离子的响应,在最优实验条件下,As3+、Pb2+在电化学活化的金电极上分别于0.18V、-0.07V产生灵敏的溶出峰,峰高与其浓度线性相关,检测限分别可达到0.5!g/L、2!g/L。该方法操作简单、干扰小、线性范围宽、灵敏度高。     

Nafion Coated Silver Amalgam Electrode for Determination of Trace Metals by Anodic Stripping Voltammetry

This paper describes characterization and application of Nafion coated solid silver amalgam electrodes to prevent surface fouling of surfactants in determination of trace metals by differential pulse anodic stripping voltammetry (DPASV). Polymer films of different thickness were tested using Nafion solutions in the range 0.25%–1%. Optimum thickness was archived using a 0.5% Nafion solution, resulting in both increased response and stability over time compared to uncoated electrodes. The influence of model surface active macromolecules was studied using triton X‐100, sodium dodecyl sulfate, dodecyl pyridinium chloride and bovine serum albumin as representatives for surfactants. The resistance to surfactants makes the studied Nafion coated solid silver amalgam electrodes an interesting alternative for practical use in environmental monitoring.     

Nafion修饰电极同位镀金膜阳极溶出伏安法测定痕量砷

金膜电极阳极溶出伏安法测定痕量砷已有报道,但铜、锑、铋存在严重干扰。本文采用Nafion修饰电极同位镀金膜阳极溶出伏安法测定痕量砷,大大提高了其选择性,铜、锑、铋分别为砷含量的6倍,3倍和6.5倍以下时,不干扰测定;测定灵敏度也较同位镀金膜电极时高。本法应用于标钢和黄河底泥中砷含量的测定,均获得满意结果。     

Nafion汞膜修饰电极用于阳极溶出伏安法测定痕量铋的研究

本文报道了Nafion汞膜修饰电极及其用于阳极溶出伏安法测定未处理尿样,水样及土样中痕量铋的研究。样品中常共存的Pb(Ⅱ)、Sb(Ⅲ )等19种阳离子及尿样中共存的有机物在实验条件下不干扰。本法不仅选择性好,而且灵敏度也较高。线性范围为2×10~(-10)～1×10~(-7)mol/L。回收率为94～105％。     

2．5次微分溶出伏安法测定水中痕量铜

报告了测定痕量铜的一种新方法。在０．０１ｍｏｌ／ＬＨＡｃ－ＮａＡｃ溶液中，铜和乙醛酸缩氨基硫脲（ＧＡＴＳＣ）形成的配合物产生一很灵敏的还原峰，峰电位是－０．３３Ｖ（ｖｓ·ＳＣＥ），铜的浓度在１．０×１０－８～２．０×１０－６ｍｏｌ／Ｌ范围内成直线关系，检测限为３．０×１０－９ｍｏｌ／Ｌ，该法用于测定水中痕量铜，结果令人满意。     

Novel Screen-Printed Gold Nano Film Electrode for Trace Mercury(II) Determination Using Anodic Stripping Voltammetry

Integrating the screen printing technique with the vacuum evaporation method, we developed a novel and disposable screen-printed gold film electrode (SPGFE) in the present work. First, a conductive silver layer, a connection graphite-carbon layer, and an insulating polymer layer were successively printed onto a flexible polyethylene terephthalate (PET) substrate. Then, a gold thin film was achieved on the scheduled vacant site by use of the vacuum evaporation method. In order to enhance the electroanalytical performance of the SPGFE, the thickness of the gold film was controlled in the range of 70–80 nm under optimum conditions. The fabricated SPGFE was applied to detect trace mercury(II) based on the square-wave anodic stripping voltammetry (SWASV). The results indicated that the proposed SPGFE exhibited higher sensitivity to trace mercury(II) than the gold disc electrode. The stripping current was linearly related to the concentration of mercury(II) in the range of 16–280 µg/L (R² = 0.9919) and 1.2–8.0 µg/L (R² = 0.9977), with a detection limit of 0.8 µg/L (S/N = 3) under 180 s accumulation. The SPGFE was further used to detect mercury in real samples, and the obtained results revealed a good agreement with those of inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectroscopy (AAS). The highly sensitive and environmental friendly electrode, as another type of “mercury-free” electrode, holds great promise in stripping measurements.     

Gold Nanoparticle Determination by Inductively Coupled Plasma-Mass Spectrometry,Anodic Stripping Voltammetry,and Flame Atomic Absorption Spectrophotometry

Gold Nanoparticles (AuNP) were measured by Inductively Coupled Plasma–Mass Spectrometry (ICP-MS), Anodic Stripping Voltammetry (SV), and flame Atomic Absorption Spectrophotometry (AAS). Experiments investigated the relationships between counts per second (ICP-MS), absorbance (AAS), or μA (SV) and Au concentrations in solutions bearing AuNP with sizes of 5, 15, and 50 nm. Similarly the impact of the solution matrix was assessed using deionized water, 1.0 M HNO₃, 1.0 M HCl (ICP-MS and AAS), and water containing the bacterium E. coli (～10⁶ organisms/mL) by all three types of instrumentation. Each instrument yielded linear calibration curves with a signal proportional to Au concentration over the concentration range 0.02 ppm to 1 ppm.The methods were all reliable when biomacromolecules or when organisms such as E.coli existed in the matrix. Comparing the limits of detection for the three methods, ICP-MS and SV were lower than AAS. Comparing cost, SV and AAS were less expensive than ICP-MS. Comparing time required for each measurement, AAS was shorter than ICP-MS and SV. In comparison of the interfering effects of E-coli, ICP-MS and AAS were less-affected, while SV was more affected. An intact E.coli or organism may be very absorptive on the electrode surface,which reduced the measured anodic currents in SV and also increased the standard deviations.     

痕量铅在草酸修饰电极上阳极溶出伏安的研究

本文对草酸修饰电极的制作、痕量铅在草酸修饰电极上的反应机理和电化学特性作了研究。采用阳极溶出伏安法,测定铅的灵敏度比玻碳电极提高7.5倍,在1.0～15.0ng·/mL铅浓度范围内溶出峰高与铅浓度呈良好的线性关系。连续测定12次变异系数为3.0％。利用草酸修饰电极对人尿中痕量铅进行了测定,结果良好。     

Copper Sensing in Alkaline Electrolyte Using Anodic Stripping Voltammetry by Means of a Lead Mediator

Anodic stripping voltammetry (ASV) is an analysis technique that permits the selective and quantitative analysis of metal ion species in solution. It is most commonly applied in neutral to acidic electrolyte largely due to inherent metal ion solubility. Bismuth (Bi) is a common film used for ASV due to its good sensitivity, overall stability and insensitivity to O₂. ASV, utilizing a Bi film, along with cadmium (Cd) and lead (Pb) as the plating mediators, has recently been adapted to determine zinc (Zn) concentrations in highly alkaline environments (30 % NaOH or 35 % M KOH). Successful analysis of Zn in alkaline relies on the ability of the hydroxide to form soluble metal anion species, such as Bi(OH)₄⁻ and Zn(OH)₄²⁻. Here, we look to extend this technique to detect and quantify copper (Cu) ions in these highly basic electrolytes. However, in general, the use of ASV to detect and quantify Cu ion concentrations is notoriously difficult as the Cu stripping peak potential overlays with that of Bi from the common Bi film electrode. Here, an ASV method for determining Cu concentration in alkaline solutions is developed utilizing Pb as a deposition mediator. As such, it was found that when analyzing Cu solutions in the presence of Pb, the stripping voltammetry curves present separate and defined Cu stripping peaks. Different analyzes were made to find the best stripping voltammetry performance conditions. As such, an accumulation time of 5 minutes, an accumulation potential of≤−1.45 V vs. Hg/HgO, and a concentration of 35 wt% KOH were determined to be the conditions that presented the best ASV results. Utilizing these conditions, calibration curves in the presence of 5.0 ppm Pb showed the best linear stripping signal correlation with an r‐squared value of 0.991 and a limit of detection (LOD) of 0.67 ppm. These results give way to evaluating Cu concentrations using ASV in aqueous alkaline solutions.     

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.     

Determination of Thallium in a Flow System by Anodic Stripping Voltammetry at a Bismuth Film Electrode

A procedure for trace thallium determination by anodic stripping voltammetry at a bismuth film electrode is presented. Measurements were performed in a flow system. The calibration graph was linear from 2×10^?9 to 3×10^?8 mol L^?1 for an accumulation time of 300 s. A detection limit for Tl⁺ following deposition time of 300 s was 6×10^?10 mol L^?1. The relative standard deviation at Tl⁺ concentration 2×10^?8 mol L^?1 was 3.9%. For determination of thallium in complex matrices the procedure for elimination of interferences from foreign ions exploiting anion exchange resin was proposed. The procedure proposed was validated by analysis of rain water certified reference material.     

Simultaneous Determination of Trace Zinc and Cadmium by Anodic Stripping Voltammetry Using a Polymeric Film Nanoparticle Self‐Assembled Electrode

A promising modified electrode was fabricated by polymerization a conductive polymer film of dipicolinic acid (DPA) onto gold nanoparticle (AuNP)‐cysteine‐gold electrode (Au). The morphology of poly(DPA)‐AuNP‐Au electrode was investigated by scanning electron microscopy (SEM). This chemically modified electrode was used for electrochemical determination of cadmium and zinc in aqueous media using differential pulse anodic stripping voltammetry. The result showed that the modified electrode could clearly resolve the anodic stripping peaks of zinc and cadmium. The linear analytical curves were obtained in the ranges of 0.020–25.0 and 0.045–17.0 µM for zinc and cadmium respectively. The limit of detections (S/N=3) were 0.008 µM for zinc and 0.015 µM for cadmium.     

Determination of Cr(VI) by Catalytic Adsorptive Stripping Voltammetry with Application of Nitrilotriacetic Acid as a Masking Agent

A selective and sensitive method for determination of traces of Cr(VI) in the presence of a large excess of Cr(III) by differential pulse catalytic adsorptive stripping voltammetry is presented. For minimization of Cr(III) interference nitrilotriacetic acid was used as a masking agent. The determinations were performed in a flow system. The calibration plot was linear from 1×10⁻¹⁰ to 1×10⁻⁸ mol L⁻¹ for accumulation time 60 s. The relative standard deviation for 3×10⁻⁹ mol L⁻¹ Cr(VI) was 4.1% (n=5). The detection limit for an accumulation time of 60 s was 4×10⁻¹¹ mol L⁻¹. The influence of common foreign ions is also presented. The performance of the method was verified by analysis of certified reference material for Cr(VI) and comparing the results of analyses of natural water samples with those obtained by another accepted electrochemical method.     

Anodic Stripping Voltammetry Using a Vibrating Electrode

This work proposes a vibrating microwire electrode as working electrode in stripping voltammetry. The vibration was found to maintain a constant and thin (1–2 μm) diffusion layer during the deposition step. The electrode vibration eliminated the need for external stirring of the solution, thus facilitating in situ detection in the environment. The vibration was effected by fixing a low‐voltage (3 V), asymmetric, electrical rotor to the working electrode (a gold microwire of either 5 or 25 μm). The sensitivity of the vibrated electrode was ca. 22×greater than stationary. Measurements of copper (4 nM) by anodic stripping voltammetry using the vibrating electrode had a low standard deviation (1% for n=6) indicating that the diffusion layer had only minor variability. The agitation mechanism was unaffected by water moving at >2 m s^?1 and by water pressure equivalent to a depth of >40 m, indicating its suitability for in situ measurements. The vibrating probe was used for in situ detection of copper by anodic stripping voltammetry to a depth of 6 m. Using a 5 min deposition time, the limit of detection for labile copper was 38 pM.     

Signal Amplification with Co(III) Protoporphyrin IX Nanoparticles and Anodic Stripping Voltammetry

Electrochemical analysis of cobalt(III) protoporphyrin IX (CoP), synthesis and characterization of CoP nanoparticles, and signal amplification for biosensor development is presented. CoP was self-assembled into nanoparticles and then released to produce over 1000 electrochemically-detectable molecules for each protein target of interest, in this case monoclonal rabbit antibody. Anodic stripping voltammetry was utilized for quantitative and sensitive detection of CoP which correlated to target protein concentration. The CoP limit of detection was 4 nM and target protein was detected at 100 pM. This combination of nanoparticle and electrochemical signal amplification could allow for sensitive, inexpensive, and portable detection of protein biomarkers.     

Determination of Trace Tin by Anodic Stripping Voltammetry at a Carbon Paste Electrode

A sensitive and selective procedure for the determination of trace tin at a carbon paste electrode was described. Each measurement cycle consisted of three steps: accumulation, reduction and stripping. The tin complex with bromopyrogallol red (BPR) was accumulated on the electrode surface in 0.10 mol/L acetate buffer (pH 4.5). After electrochemical reduction of Sn(II) had been carried out, the reoxidation wave of Sn(0) appeared at ?0.69 V (vs. SCE) on scanning the potential in the positive direction in 4.0 mol/L HCl. For a preconcentration time of 2 min, the detection limit was 0.06 μg/L (5×10^?10 mol/L ) and the linear range was from 0.1 to 50 μg/L. The proposed method was applied to the determination of tin in canned food and waste water samples with satisfactory results.     

Renewable Ceramic (TiN) Ring Electrode in Stripping Voltammetry. Determination of Pb(II) Without Removal of Oxygen

Characteristic features of the process of Pb(II) reduction and oxidation at a renewable ceramic ring electrode (RCRE) were studied by stripping voltammetry. The main constituents of the RCRE are: a specially constructed TiN ring electrode, a silver sheet used as silver counter/quasi‐reference electrode and a silicon O‐ring are fastened together in a polypropylene body. The renovation of this electrode is carried out through mechanical removal of solid contaminants and electrochemical activation in the electrolyte which fills the RCRE body. The optimal measurement conditions, composition of supporting electrolyte and procedures of the electrode activation were selected. The measurements were carried out from nondeaerated solutions. As shown on selected examples, RCRE exhibits good performance in underpotential deposition stripping voltammetry (UPD‐SV) applied for the determination of lead(II) in synthetic solutions with and without surfactants and in certified reference materials. The peak current is proportional to the concentration of lead(II) over the range 2×10^?9–1×10^?7 mol L^?1, with a 3σ detection limit of 1×10^?9 mol L^?1 with an accumulation time of 30 s. The obtained results showed good reproducibility, (RSD=2–5%; n=5) and reliability.     

The Cyclic Renewable Mercury Film Silver Based Electrode for Determination of Uranium(VI) Traces Using Adsorptive Stripping Voltammetry

The new cyclic renewable mercury film silver based electrode (Hg(Ag)FE), applied for the determination of uranium(VI) traces using differential pulse adsorptive cathodic stripping voltammetry (DP AdCSV) is presented. The Hg(Ag)FE electrode with a surface area adjustable from 1.1 to 12 mm² is characterized by very good surface reproducibility (≤2%) and long‐term stability (more than 2 thousand measurement cycles). The mechanical refreshing of mercury film is realized in the simple constructed device, in a time shorter than 1–2 seconds. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimized. The calibration graph is linear from 0.4 nM (95 ng L^?1) to 250 nM (60 μg L^?1) for an accumulation time of t_acc=20 s, with correlation coefficient of 0.9996. For a Hg(Ag)FE with a surface area of 2.7 mm² the detection limit for an accumulation time of 120 s is as low as 12 ng L^?1. The repeatability of the method at a concentration level of the analyte as low as 2.4 μg L^?1, expressed as RSD is 2.5% (n=7). The proposed method was successfully applied and validated by studying the recovery of U(VI) from spiked river water and sediment samples.