Development of a sequential injection anodic stripping voltammetry (SI-ASV) method for determination of Cd(II), Pb(II) and Cu(II) in wastewater samples from coatings industry

This paper describes the development and validation of a sequential injection (SI) anodic stripping voltammetry (ASV) method using the hanging mercury drop electrode for accumulation of the heavy metal cations Cu(II), Pb(II) and Cd(II). The method was applied to wastewater samples after proper acid digestion in open vessels to eliminate matrix effects. For a deposition time of 90 s at the flow rate of 10 μl s⁻¹, the detection limits of the method were 0.06, 0.09 and 0.16 μmol L⁻¹ for Cd, Pb and Cu, respectively. Under these conditions the linear dynamic range was between 0.20 and 9.0 μmol L⁻¹ and the sampling frequency was 30 analyses per hour. The relative standard deviation of the method was 3%(n=7) at the concentration level of 2.0 μmol L⁻¹. The accuracy of the method was evaluated by spiking the samples with known amounts of the metal cations, and by comparison with an independent analytical technique, the inductively coupled plasma atomic emission spectroscopy (ICP-AES). Average recoveries were around of 84%, and the results showed no evidence of systematic errors in comparison to the ICP-AES.     

On-line coupling of sequential injection lab-on-valve to differential pulse anodic stripping voltammetry for determination of Pb in water samples

Sequential injection lab-on-valve (LOV) was first proposed for analyzing ultra-trace amounts of Pb using differential pulse anodic stripping voltammetry (DPASV) with a miniaturized electrochemical flow cell fabricated in the LOV unit. Deposition and stripping processes took place between the renewable mercury film carbon paste electrode and sample solution, the peak current was employed as the basis of quantification. The mercury film displayed a long-term stability and reproducibility for at least 50 cycles before next renewal, the properties of integrated miniature LOV unit not only enhanced the automation of the analysis procedure but also declined sample/reagent consumption. Potential factors that affect the present procedure were investigated in detail, i.e., deposition potential, deposition time, electrode renewable procedure and the volume of sample solution. The practical applicability of the present procedure was demonstrated by determination of Pb in environmental water samples.     

Low-level determination of silicon in steels by anodic stripping voltammetry on a hanging mercury drop electrode

The sensitive differential pulse anodic stripping voltammetry (DPASV) proposed originally by Ishiyama et al. (2001) has been revised and improved to allow the accurate measurement of silicon on a hanging mercury drop electrode (HMDE) instead of a glassy carbon electrode. We assessed the rate of formation of the partially reduced β-silicododecamolybdate and found that metallic mercury promotes the reaction in the presence of a large concentration of Fe³⁺. The scope of the method has been broadened by carrying out the measurements in the presence of a constant amount of Fe³⁺. The limit of detection (LOD) of the method described in the present paper is 100 μg Si g⁻¹ of steel, with a relative precision ranging from 5% to 12%. It can be further enhanced to 700 ng Si g⁻¹ of steel provided the weight of the sample, the dilution factors, the duration of the electrolysis and the ballast of iron are adequately revised. The tolerance to several interfering species has been examined, especially regarding Al³⁺, Cr³⁺ and Cr VI species. The method was validated using four low-alloy ferritic steels certified by the National Institute of Standards and Technology (NIST). Its application to nickel base alloys as well as to less complicated matrixes is straightforward. It has also been successfully applied to the determination of free silicon into silicon carbide nano-powder.     

Sequential injection monosegmented flow voltammetric determination of cadmium and lead using a bismuth film working electrode

A cost-effective sequential injection monosegmented flow analysis (SI-MSFA) with anodic stripping voltammetric (ASV) detection has been developed for determination of Cd(II) and Pb(II). The bismuth film working electrode (BiFE) was employed for accumulative preconcentration of the metals by applying a fixed potential of −1.10 V versus Ag/AgCl electrode for 90 s. The SI-MSFA provides a convenient means for preparation of a homogeneous solution zone containing sample in an acetate buffer electrolyte solution and Bi(III) solution for in situ plating of BiFE, ready for ASV measurement at a flow through thin layer electrochemical cell. Under the optimum conditions, linear calibration graphs in range of 10-100 μg L⁻¹ of both Cd(II) and Pb(II) were obtained with detection limits of 1.4 and 6.9 μg L⁻¹ of Cd(II) and Pb(II), respectively. Relative standard deviations were 2.7 and 3.1%, for 11 replicate analyses of 25 μg L⁻¹ Cd(II) and 25 μg L⁻¹ Pb(II), respectively. A sample throughput of 12 h⁻¹ was achieved with low consumption of reagent and sample solutions. The system was successfully applied for analysis of water samples collected from a draining pond of zinc mining, validating by inductively coupled plasma-optical emission spectroscopy (ICP-OES) method.     

An automatic system for acidity determination based on sequential injection titration and the monosegmented flow approach

An automatic sequential injection system, combining monosegmented flow analysis, sequential injection analysis and sequential injection titration is proposed for acidity determination. The system enables controllable sample dilution and generation of standards of required concentration in a monosegmented sequential injection manner, sequential injection titration of the prepared solutions, data collecting, and handling. It has been tested on spectrophotometric determination of acetic, citric and phosphoric acids with sodium hydroxide used as a titrant and phenolphthalein or thymolphthalein (in the case of phosphoric acid determination) as indicators. Accuracy better than |4.4|% (RE) and repeatability better than 2.9% (RSD) have been obtained. It has been applied to the determination of total acidity in vinegars and various soft drinks. The system provides low sample (less than 0.3 mL) consumption. On average, analysis of a sample takes several minutes.     

Refreshable mercury film silver based electrode for determination of chromium(VI) using catalytic adsorptive stripping voltammetry

The refreshable mercury film silver based electrode Hg(Ag)FE applied for determination of Cr(VI) traces using catalytic adsorptive striping voltammetry (CAdSV) will be presented. The film electrode is characterized by its very good surface reproducibility (not less than 2%) and long-term stability (1500–2000 measurement cycles). The mechanical refreshing of mercury film is realized in the specially constructed device, in a time shorter than 1–2 s.

In the paper, it will be proved that a mechanically weak hanging mercury drop electrode (HMDE) may be substituted by mercury film Hg(Ag)FE electrode with a surface area adjustable from 1.5 to 12 mm². For the electrode surface 4 mm² the detection limit obtained for Cr(VI) was 0.19 nM, while the linearity range measured for a 20 s accumulation time was between 0.5 and 50 nM. The relative standard deviation (R.S.D.) in determination of Cr(VI) varied from 1 to 5%. The influence of the excess of Cr(III) on determination of Cr(VI) was analyzed using samples from the Dobczyce reservoir spiked with known amounts of Cr(VI) and Cr(III).     

Fullerene-based anodic stripping voltammetry for simultaneous determination of Hg(II), Cu(II), Pb(II) and Cd(II) in foodstuff

Various carbon nanomaterials for use in anodic stripping voltammetric analysis of Hg(II), Cu(II), Pb(II) and Cd(II) are screened. Graphene, carbon nanotubes, carbon nanofibers and fullerene (C₆₀), dispersed in chitosan (Chit) aqueous solution, are used to modify a glassy carbon electrode (GCE). The fullerene-chitosan modified GCE (C₆₀-Chit/GCE) displays superior performance in terms of simultaneous determination of the above ions. The electrodes and materials are characterized by electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The excellent performance of C₆₀-Chit/GCE is attributed to the good electrical conductivity, large surface area, strong adsorption affinity and unique crystalline structure of C₆₀. Using differential pulse anodic stripping voltammetry, the assay has the following features for Hg(II), Cu(II), Pb(II) and Cd(II), respectively: (a) Peak voltages of +0.14, ?0.11, ?0.58 and???0.82 V (vs SCE); (b) linear ranges extending from 0.01–6.0 μM, 0.05–6.0 μM, 0.005–6.0 μM and 0.5–9.0 μM; and (c), detection limits (3σ method) of 3 nM (0.6 ppb), 14 nM (0.9 ppb), 1 nM (0.2 ppb) and 21 nM (2.4 ppb). Moreover, the modified GCE is well reproducible and suitable for long-term usage. The method was successfully applied to the simultaneous determination of these ions in spiked foodstuff.

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Graphical abstract Compared with graphene, carbon nanotubes and carbon nanofibers, an electrode modified with fullerene in chitosan electrode displays superior performance for the simultaneous anodic stripping voltammetric detection of Hg(II), Cu(II), Pb(II) and Cd(II).

     

Exploiting flow injection and sequential injection anodic stripping voltammetric systems for simultaneous determination of some metals

Flow injection (FI) and sequential injection (SI) systems with anodic stripping voltammetric detection have been exploited for simultaneous determination of some metals. A pre-plated mercury film on a glassy carbon disc electrode was used as a working electrode in both systems. The same film can be repeatedly applied for at least 50 analysis cycles, thus reducing the mercury consumption and waste. A single line FI voltammetric system using an acetate buffer as a carrier and an electrolyte solution was employed. An injected standard/sample zone was mixed with the buffer in a mixing coil before entering a flow cell. Metal ions were deposited on the working electrode by applying a potential of −1.1 V vs Ag/AgCl reference electrode. The stripping was performed by anodically scanning potential of working electrode to +0.25 V, resulting a voltammogram. Effects of acetate buffer concentration, flow rate and sample volume were investigated. Under the selected condition, detection limits of 1 μg l⁻¹ for Cd(II), 18 μg l⁻¹ for Cu(II), 2 μg l⁻¹ for Pb(II) and 17 μg l⁻¹ for Zn(II) with precisions of 2–5% (n=11) were obtained. The SI voltammetric system was similar to the FI system and using an acetate buffer as a carrier solution. The SI system was operated by a PC via in-house written software and employing an autotitrator as a syringe pump. Standard/sample was aspirated and the zone was then sent to a flow cell for measurement. Detection limits for Cd(II), Cu(II), Pb(II) and Zn(II) were 6, 3, 10 and 470 μg l⁻¹, respectively. Applications to water samples were demonstrated. A homemade UV-digester was used for removing organic matters in the wastewater samples prior to analysis by the proposed voltammetric systems.     

Decomposition of vegetables for determination of Zn,Cd, Pb and Cu by stripping voltammetry

A simple and accurate digestion method using nitric acid, perchloric acid and hydrogen peroxide has been developed for use in trace analysis for heavy metals in vegetables by differential pulse anodic stripping voltammetry. The recovery of the metals from the samples is lower if the hydrogen peroxide is omitted from the digestion mixture. Standard reference materials have been analysed satisfactorily by this method.     

Differential-pulse voltammetric determination of low μg l cyanide levels using EDTA, Cu(II) and a hanging mercury drop electrode

The proposed method for cyanide determination at the ultratrace level by differential pulse voltammetry is based in the sensitivity enhancement obtained when both Cu(II) and EDTA are present in the background electrolyte. Comparison of the detection limits and linear dynamic ranges using the conventional borate (pH 9.75), and the proposed borate-EDTA–Cu(II) background electrolytes was carried out. Best results have been obtained with the addition of 0.5 mmol l⁻¹ EDTA and 0.02 mmol l⁻¹ of Cu(II), which allow a detection limit of 1.7 μg l⁻¹ CN⁻ (65 nmol l⁻¹ — absolute detection limit 34 ng) with a precision better than ±2% for a 40 μg l⁻¹ level. Calibration range extended from detection limit up to 100 μg l⁻¹. Cyclic voltammetry indicates that the measured cyanide peak is obtained when the electrogenerated CuCN adsorbed onto the hanging mercury drop electrode surface, is oxidised at positive going potential scan. The method has been successfully applied to various industrial waste waters such as metal-finishing waste waters, water/sand mixtures from cleaning processes of coke production, leachates from wastes obtained from electrolytic cells of aluminium production, and liquors from gold extraction industry. Results obtained by the proposed method showed good agreement with those obtained by the standard methods (ion-selective potentiometry and the spectrophotometric pyridine method).     

Microdroplet anodic stripping voltammetry at the in situ preparing antimony-modified rotating disk electrode for determination of Cd(II) and Pb(II)

A simple electroanalytical method for Cd(II) and Pb(II) detection based on differential pulse anodic stripping voltammetry (DPSV) with in situ prepared antimony-modified glassy carbon rotating disk electrode (in situ Sb-GC-RDE) was developed. The electrochemical detection was performed in a microdroplet (50 μL) of 0.01 M hydrochloric acid that is placed between the electrode surface (top) and a Parafilm®-covered glass slide to maintain a hydrophobic surface (bottom). This method includes a preconcentration process using a membrane filter (MF). The target metal ions were complexed with 1-(2-pyridylazo)-2-naphthol (PAN) as a chelating agent, which was accumulated on the MF via filtration. The RDE microdroplet anodic stripping voltammetry was suitable for the elution and determination of metal ions accumulated on the MF. The in situ preparation of antimony-modified electrode allows the use of common GC electrode with high performance. The detection limits for Cd(II) and Pb(II) were 1.4 and 1.1 μg/L, respectively. The proposed method was successfully used in natural water samples for the simultaneous determination of Cd(II) and Pb(II).     

Comparison of digestion procedures for the determination of heavy metals (Cd, Cu, Pb) in blood by anodic stripping voltammetry

Summary The simultaneous determination of cadmium, lead and copper in whole blood by anodic stripping voltammetry is described. Different digestion procedures given in literature were examined. In addition, a sample pretreatment method which did not involve digestion was studied. Based on the experience with these methods two digestion procedures were developed. They utilize digestion with mixtures of nitric, perchloric and sulphuric acids, with and without pressure, respectively. Both methods are suitable for routine analysis of about 20 blood samples per day. Special attention was focussed on the completeness of the digestion, and the magnitude of the blank values. Low blank values and a high sensitivity allowed the determination of cadmium at the sub-ppb level with an electrolysis time of 5 min. The methods, which were controlled by recovery tests, were used to analyze blood samples from unexposed persons, and from workers suspected of exposure to cadmium.

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Vergleich von Aufschlußverfahren für die Bestimmung von Schwermetallen (Cd, Cu, Pb) in Blut durch Anodic Stripping Voltammetrie

Zusammenfassung Verschiedene in der Literatur beschriebene Aufschlußverfahren wurden untersucht und zusätzlich ein Probenvorbereitungsverfahren ohne Aufschluß geprüft. Aufgrund der mit diesen Methoden gewonnenen Erfahrungen wurden zwei Aufschlußverfahren entwickelt, bei denen Mischungen von Salpeter-, Perchlor- und Schwefelsäure mit und ohne Anwendung von Druck eingesetzt werden. Beide Methoden eignen sich für die Routineuntersuchung von etwa 20 Blutproben je Tag. Besondere Aufmerksamkeit wurde der Vollständigkeit des Aufschlusses und der Größe der Blindwerte gewidmet. Niedrige Blindwerte und hohe Empfindlichkeit erlaubten die Bestimmung von Cadmium im sub-ppb-Bereich mit einer Elektrolysezeit von 5 min. Die Methoden wurden durch Wiederauffindungstests geprüft und für die Blutuntersuchung von Personen, die der Einwirkung von Cd ausgesetzt waren, sowie solchen, bei denen dies nicht der Fall war, angewendet.

     

Optimization of square wave anodic stripping voltammetry (SWASV) for the simultaneous determination of Cd,Pb, and Cu in seawater and comparison with differential pulse anodic stripping voltammetry (DPASV)

Square wave anodic stripping voltammetry (SWASV) was optimized for the simultaneous determination of Cd, Pb and Cu in coastal seawater samples. Background subtraction was adapted to improve peak detection and quantification. Optimum background voltammograms were obtained by applying a 7.5 s equilibration potential at -975 mV (vs. Ag/AgCl, 3M KCl) before starting the background scan. Voltammetric scan parameters were optimized to obtain maximum sensitivity while retaining good peak resolution and discrimination from background. Optimal parameters were: frequency 100 Hz, pulse amplitude 25 mV, current sampling delay time 2 ms, step height 8 mV. The sensitivity of optimized SWASV proved to be more than double that of differential pulse anodic stripping voltammetry (DPASV), and analysis time was halved. Samples containing around 13 (Cd), 30 (Pb), 200 (Cu) ng/l (typical averages of the coastal area of the Marche region) can be analyzed using a 5 min deposition time and the total analysis time using three standard additions is about 1 h and half, excluding the mercury film preparation and the outgassing of the sample, which can be made in parallel using a second cell cup.     

Continuous flow and flow injection stripping voltammetric determination of silver(I), mercury(II), and bismuth(III) at a bulk modified graphite tube electrode

The epoxy-impregnated graphite tube electrode bulk modified with 2-mercaptobenzoxazole, employed in a wall-jet configuration, was found to be useful for the continuous flow and flow injection stripping voltammetric determinations of Ag^I, Hg^II and Bi^III. For continuous flow, detection limits for Ag^I, Hg^II and Bi^III were 1.8 × 10⁻¹⁰ M, 1.9 × 10⁻⁹ M and 9.5 × 10⁻⁹ M, respectively (10 min accumulation, S/N = 3). Precisions for 5.00 × 10⁻⁹ M Ag^I, 1.00 × 10⁻⁸ M Hg^II and 1.00 × 10⁻⁷ M Bi^III were 10.5%, 5.77 % and 7.90% (relative standard deviations, n = 6), respectively. In the case of flow injection stripping, with a 500 μL injection loop, detection limits of 0.59 ng, 2.0 ng and 120 ng were obtained for Ag^I, Hg^II and Bi^III, respectively (S/N = 3). Selected metal ions, inorganic and organic substances were investigated for interferences. The electrode was tested with a certified sample and then applied to the determinations of the metal ions in a urine and a sea-water sample.     

A novel method for the simultaneous determination of Pb (II), Cd (II) and Zn (II) in environmental water samples

A novel UV-VIS spectrophotometric method was developed in this study by using solid phase extraction procedure for the simultaneous preconcentration, separation and determination of trace levels of Pb (II), Cd (II) and Zn (II) ions in various water samples by using Amberlite N,N-bis(salicylidene)cyclohexanediamine (SCHD) resin. This study presents the results of experimental procedures carried out like the adsorption of analytes to the resin, influences of some analytical parameters that effect the recovery such as pH, sample volume, sample flow rate, eluent type and concentration, eluent volume, eluent flow rate and the effects of alkaline metals, earth alkaline metals and some other transition metals. The analytes in the samples with the adjusted pH range of 4–7 were adsorbed on XAD-4-SCHD resin and eluted by using 1.0 mol L^?1 nitric acid. The amounts of ions were determined by using UV-VIS spectrometer. The limits of detection were 0.03, 0.07 and 0.05 µg mL^?1 for Pb (II), Cd (II) and Zn (II), respectively. The accuracy of the method was assured by the analysis of the certified standard water sample NW-TMDA-70.2 and the observed recoveries were above 93%. Different environmental water samples that contain trace amounts of Pb (II), Cd (II) and Zn (II) were analysed by using the method developed in this study. Same samples were also analysed by ICP-MS for comparison and almost the similar results were observed. The method developed in this study was successfully applied to the various environmental water samples to determine the trace levels of Pb (II), Cd (II) and Zn (II) ions.     

Digestion-free determination of heavy metals (Pb, Cd, Cu) in honey using anodic stripping differential pulse voltammetry and potentiometric stripping analysis

Experiments have been carried out to assess the potential of differential pulse voltammetry and potential stripping analysis for determining Pb, Cu and Cd directly in dissolved honey samples using a flow-through cell. With the hanging mercury drop electrode Pb alone can be determined only if the electrode is first modified in-situ with Triton X 100 to increase the separation between the Pb peak and a broad, interfering adsorption peak which overlaps the Cu peak. If the (more sensitive) thin film mercury electrode is used the interference encountered is less so also Cu and Cd can be determined. With potentiometric stripping analysis Cu and Pb can be determined using normal procedures. The determination of Cd, however, can only be carried out if the concentration of the oxidizing agent [Hg(II)] in solution is decreased. A good agreement has been obtained between the values found and those obtained after high pressure digestion of the samples.     

Spectrophotometric determination of Cu(II) with sequential injection analysis

A sequential injection system, based on the reaction of Cu(II) with diethyldithiocarbamate (DDTC), was developed for the determination of Cu(II) in plant food and water samples. The extraction procedure, generally used to extract the Cu(II)–DDTC complex for subsequent analysis was eliminated in this procedure. The complex was detected spectrophotometrically in aqueous solutions at 460 nm. The physical and chemical parameters depicting the system were studied to obtain optimum conditions for sample analysis. The system developed is fully computerized and able to monitor Cu(II) in samples at seven samples per hour with a relative standard deviation of <4.50%. The calibration curve is linear from 0.5–5.0 mg/l with a detection limit of 0.2 mg/l. Interferences were reduced by introducing multiple flow reversals, to increase mixing between the reagent and sample zones, and subsequently enhance working of the masking agents (EDTA/citrate).     

Antimony film screen-printed carbon electrode for stripping analysis of Cd(II), Pb(II), and Cu(II) in natural samples

An in-situ antimony film screen-printed carbon electrode (in-situ SbSPCE) was successfully used for the determination of Cu(II) simultaneously with Cd(II) and Pb(II) ions, by means of differential pulse anodic stripping voltammetry (DPASV), in a certified reference groundwater sample with a very high reproducibility and good trueness. This electrode is proposed as a valuable alternative to in-situ bismuth film electrodes, since no competition between the electrodeposited copper and antimony for surface sites was noticed. In-situ SbSPCE was microscopically characterized and experimental parameters such as deposition potential, accumulation time and pH were optimized. The best voltammetric response for the simultaneous determination of Cd(II), Pb(II) and Cu(II) ions was achieved when deposition potential was −1.2 V, accumulation time 120 s and pH 4.5. The detection and quantification limits at levels of μg L⁻¹ suggest that the in-situ SbSPCE could be fully suitable for the determination of Cd(II), Pb(II) and Cu(II) ions in natural samples.     

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.     

Square wave adsorptive cathodic stripping voltammetry automated by sequential injection analysis Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L⁻¹ Britton-Robinson buffer (pH 10) in 0.25 mol L⁻¹ NaNO₃. The homogenized mixture is injected at a flow rate of 10 μL s⁻¹ toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from −0.3 to −1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV. The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mg L⁻¹, with detection and quantification limits of 2 and 7 μg L⁻¹, respectively. The sampling throughput is 25 h⁻¹ if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h⁻¹ if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered.