Analytical procedure for the simultaneous voltammetric determination of trace metals in food and environmental matrices. Critical comparison with atomic absorption spectroscopic measurements

An analytical procedure fit for the simultaneous determination of copper (II), chromium(VI), thallium(I), lead(II), tin(II), antimony(III), and zinc(II) by square wave anodic stripping voltammetry (SWASV) in three interdependent environmental matrices involved in foods and food chain as meals, cereal plants and soils is described. The digestion of each matrix was carried out using a concentrated HCl-HNO3-H2SO4 (meals and cereal plants) and HCl-HNO3 (soils) acidic attack mixtures. 0.1 mol/L dibasic ammonium citrate pH 8.5 was employed as the supporting electrolyte. The voltammetric measurements were carried out using, as working electrode, a stationary hanging mercury drop electrode (HMDE) and a platinum electrode and an Ag/AgCl/KClsat electrode as auxiliary and reference electrodes, respectively. The analytical procedure was verified by the analyses of the standard reference materials: Wholemeal BCR-CRM 189, Tomato Leaves NIST-SRM 1573a and Montana Soil Moderately Elevated Traces NIST-SRM 2711. For all the elements in the certified matrix, the precision as repeatability, expressed as relative standard deviation (Sr %) was lower than 5%. The accuracy, expressed as percentage relative error (e %) was of the order of 3-7%, while the detection limits were in the range 0.015-0.103 microg/g. Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meal samples, cereal plants and soils samples drawn in sites devoted to agricultural practice. A critical comparison with spectroscopic measurements is also discussed.     

Simultaneous Determination of Aluminum and Iron in High Salt Content Matrices by Adsorptive Stripping Voltammetry. Application to Dialysis Fluids

A new analytical procedure for the simultaneous determination of aluminum(III) and iron(II) in two kinds of dialysis fluids (peritoneal and hemodialysis fluids) by differential pulse adsorptive stripping voltammetry (DPAdSV) is described. The voltammetric measurements were performed using, as working electrode, a stationary mercury electrode, and a platinum electrode and a Ag|AgCl|KCl_(sat.) electrode as auxiliary and reference electrodes, respectively, employing acetate buffer solutions at different pH as supporting electrolyte. As complexing agents, Solochrome Violet RS, Palatine Chrome Black 6BN, Chromazurol S and Eriochrome Black T were employed. For both elements, the accuracy, expressed as relative recovery R%, was very satisfactory being in the range 94–105%, the precision as repeatability, expressed as relative standard deviation s_r%, was lower than 6%, while the limits of detection were of the order of a few units of μg/L. The analytical voltammetric procedure has been validated by comparison with spectroscopic (graphite furnace atomic absorption spectroscopy, GFAAS) measurements.     

Measurement of voltammetric peak area and resolution of overlapping peaks in the simultaneous determination of copper, lead, cadmium, and nickel in environmental matrixes

Peak area was used for the simultaneous determination of copper(II), lead(II), cadmium(II), and nickel(II) in environmental matrixes by differential pulse voltammetry. The voltammetric measurements were performed with a conventional 3-electrode cell and an ammonia-ammonium chloride buffer, pH 9.1, as the supporting electrolyte. The analytical procedure was verified first in aqueous reference solutions and later by analysis of the standard reference materials Estuarine Sediment BCR-CRM 277 and River Sediment BCR-CRM 320. The precision and accuracy of the method, expressed as the relative standard deviation and the relative error, respectively, were <5% in all cases; the detection limit for each element under the experimental conditions used was in the range 1-5 microg/L. In the case of mutual interference between neighboring elements, an analytical procedure is proposed that is based on the standard additions technique, which allows the resolution of the overlapping voltammetric peaks.     

Simultaneous square wave anodic stripping voltammetric determination of Cr, Pb, Sn, Sb, Cu, Zn in presence of reciprocal interference: application to meal matrices

An analytical procedure for simultaneously determining chromium(VI), lead(II), tin(II), antimony(III), copper(II) and zinc(II) by square wave anodic stripping voltammetry (SWASV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal is described.The digestion of each matrix was carried out using a concentrated HCl–HNO₃–H₂SO₄ acidic attack mixture. Dibasic ammonium citrate buffer solution pH 6.5 was employed as the supporting electrolyte. The voltammetric measurements were carried out using, as working electrode, a stationary hanging mercury drop electrode (HMDE) and a platinum electrode and an AgAgClKCl_sat electrode as auxiliary and reference electrodes, respectively. The analytical procedure was verified by the analysis of the standard reference materials Wholemeal BCR-CRM 189, Wheat Flour NIST-SRM 1567a and Rice Flour NIST-SRM 1568a.For all the elements in the certified matrix, the precision as repeatability, expressed as relative standard deviation (s_r) was of the order of 3–5%. The accuracy, expressed as relative error (e) was generally of the order of 3–6%, while the detection limits were lower than 0.123 μg/g.In the presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique.Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meals sampled on market for sale. A critical comparison with spectroscopic measurements is also discussed.     

Cathodic and anodic stripping voltammetry: simultaneous determination of As-Se and Cu-Pb-Cd-Zn in the case of very high concentration ratios

Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II) and zinc(II) are determined in environmental matrices. The voltammetric measurements were carried out using a conventional three-electrode cell and the ammonia-ammonium chloride buffer pH 9.3 as supporting electrolyte. The analytical procedure was verified by the analysis of the standard reference materials Estuarine Sediment BCR-CRM 277 and River Sediment BCR-CRM 320. The precision, expressed as relative standard deviation (s(r)), and the accuracy, expressed as relative error, were, in all cases, less than 5%; the detection limits, for each element and in the experimental conditions employed, were around 10(-9) M. The standard addition technique significantly improved the resolution of the voltammetric method, even in the case of very high metal concentration ratios.     

Determination of Se, As, Cu, Pb, Cd, Zn and Mn by anodic and cathodic stripping voltammetry in marine environmental matrices in the presence of reciprocal interference. Proposal of a new analytical procedure

Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II), zinc(II) and manganese(II) have been determined in environmental matrices by differential pulse cathodic (DPCSV) and anodic (DPASV) stripping voltammetry. The voltammetric measurements were carried out using a conventional three-electrode cell and the ammonia–ammonium chloride buffer (pH 9.4) as the supporting electrolyte. The analytical procedure was verified by the analysis of the standard reference materials: Sea Water BCR-CRM 403; Lagarosiphon Major BCR-CRM 060; and Cod Muscle BCR-CRM 422. The precision, expressed as relative standard deviation, and the accuracy, expressed as relative error, were, in all cases, lower than 5%; the detection limits, for each element in the experimental conditions employed, was approximately 10⁻⁹ M. The standard addition technique significantly improved the resolution of the voltammetric method, even in the case of very high metal concentration ratios.     

Platinum(II), palladium(II), rhodium(III) and lead(II) voltammetric determination in sites differently influenced by vehicle traffic

The present work reports analytical results relevant to voltammetric determination of Pt(II), Pd(II), Rh(III) [Platinum Group Metals (PGMs)] and Pb(II) in superficial water sampled in sites differently influenced by vehicle traffic, especially considering their temporal behaviour. For all the elements, in addition to detection limits, precision, expressed as relative standard deviation (s(r) %) and accuracy, expressed as percentage recovery (R %) are also reported. In all cases they show to be good, being the former lower than 6% and the latter in the range 94-105%. A critical comparison with spectroscopic measurements is also discussed.     

Determination of iron(II) with chemically-modified carbon-paste electrodes

The utility of carbon-paste electrodes modified with 2,2'-bipyridyl and Nafion for the differential pulse voltammetric determination of iron(II) in aqueous medium is demonstrated. The method is based on formation of the 2,2'-bipyridyl complex of iron(II) and its accumulation by the Nafion. The differential pulse voltammetric response of the accumulated complex is used as the analytical signal. The response was evaluated with respect to carbon-paste composition, preconcentration time, pH, iron(II) concentration and other variables. A 3-min accumulation period permits measurement of iron(II) down to 10(-8)M, and a relative standard deviation of 3.8% for 2 x 10(-6)M iron(II). Rapid and convenient chemical renewal allows use of a single modified carbon-paste electrode in multiple analytical measurements over several days. The proposed procedure was applied to the determination of iron in certified standard reference materials and trace iron in natural waters.     

Antimony Film Electrode Prepared In Situ in Hydrogen Potassium Tartrate in Anodic Stripping Voltammetric Trace Detection of Cd(II), Pb(II), Zn(II), Tl(I), In(III) and Cu(II)

An antimony film electrode (SbFE) was prepared in situ on a glassy carbon support and in a new supporting electrolyte, a saturated solution of hydrogen potassium tartrate in which Sb(III) ions were complexed using tartrate. Its performance in anodic stripping voltammetric (ASV) determination of Cd(II), Pb(II), Zn(II), Tl(I), In(III) and Cu(II) traces was examined. It was found that 1.2 mg/L of Sb(III) yields the finest quality SbFE for analytical purposes. The procedure with in situ SbFE ensures well‐defined anodic stripping voltammetric curves of the investigated elements, low detection limits (0.5–3.8 µg/L), good reproducibility (1–5 %) and satisfactory sensitivity (32–184 nA/(µg/L)).     

Trace level voltammetric determination of manganese, iron and chromium in real samples in the presence of each other

The determination of manganese in the presence of iron and chromium by differential pulse voltammetry and fundamental harmonic alternating current voltammetry was compared, including the case of very high element concentration ratios. The voltammetric measurements were carried out using a stationary mercury electrode in ammonia-ammonium chloride buffer (pH 9.6). The analytical procedure was verified by the analysis of the standard reference materials Portland Cement BCS 372, Spectrographic Zinc Spelter NBS-SRM 631, Stainless Steel (AISI 321) NBS-SRM 121d and Highly Alloyed Steel Eurostandard 281-1. Precision and accuracy, expressed as relative standard deviation and relative error respectively, were of the order of 3-5%, while the detection limit for each element was around 1 x 10(-9) M. The standard addition technique improved the resolution of the voltammetric methods, within a maximum experimental error of 5%, even in the case of very high concentration ratios, that is outside the non-interference concentration ratios 69:1 >c(Fe):c(Mn) > 1:74; 35:1 > c(Fe):c(Cr) > 1:30 and 63:1 > c(Fe):c(Mn) > 1:65; 32:1 > c(Fe):c(Cr) > 1:31 for the differential pulse and alternating current techniques respectively, extrapolating the linear section of the i(p) vs. concentration analytical calibration function for the element present at the lowest concentration. In contrast, the element with the greatest concentration was determined by the relevant calibration curve.     

Heavy Metals in Matrices of Food Interest: Sequential Voltammetric Determination at Trace and Ultratrace Level of Copper,Lead, Cadmium,Zinc, Arsenic,Selenium, Manganese and Iron in Meals

The voltammetric methods are very suitable and versatile techniques for the simultaneous metal determination in complex matrices. The present work, regarding the sequential determination of Cu(II), Pb(II), Cd(II), Zn(II) by square‐wave anodic stripping voltammetry (SWASV), As(III), Se(IV) by square‐wave cathodic stripping voltammetry (SWCSV) and Mn(II), Fe(III) by square‐wave voltammetry (SWV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal, are an interesting example of the possibility to sequentially determine each single element in real samples. Besides the set up of the analytical method, particular attention is aimed either at the problem of possible signal interference or to show that, using the peak area A_p as instrumental datum, it is possible to achieve lower limits of detection. The analytical procedure was verified by the analysis of the standard reference materials: Wholemeal BCR‐CRM 189, Wheat Flour NIST‐SRM 1567a and Rice Flour NIST‐SRM 1568a. Precision, as repeatability, and accuracy, expressed as relative standard deviation and relative error, respectively, were lower than 6% in all cases. In the presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique. Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meals sampled on market for sale. A critical comparison with spectroscopic measurements is also discussed.     

Determination of platinum-group metals and lead in vegetable environmental bio-monitors by voltammetric and spectroscopic techniques: critical comparison

This paper reports voltammetric sequential determination of Pt(II), Pd(II), and Rh(III), by square-wave adsorption stripping voltammetry (SWAdSV), and Pb(II), by square-wave anodic stripping voltammetry (SWASV), in vegetable environmental matrices. Analytical procedures were verified by the analysis of the standard reference materials: Olive Leaves BCR-CRM 062 and Tomato Leaves NIST-SRM 1573a. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were always less than 6% and the limits of detection (LOD) for each element were below 0.096 g g^–1. Once set up on the standard reference materials, the analytical procedure was transferred and applied to laurel leaves sampled in proximity to a superhighway and in the Po river mouth area. A critical comparison with spectroscopic measurements is discussed.     

Overlapping voltammetric peaks—an analytical procedure for simultaneous determination of trace metals. Application to food and environmental matrices

Voltammetric methods are very suitable, versatile and rapid techniques for simultaneous determination of metals in complex matrices. The present work, determination of Cu(II), Sn(II), Sb(III), Tl(I), and Pb(II) by square-wave anodic-stripping voltammetry and Cr(VI) by square-wave adsorptive-stripping voltammetry, is an interesting example of the possibility of simultaneous determination of each single element in food and environmental samples, even in the presence of reciprocal interference. Dibasic ammonium citrate, pH 6.3 or 8.2, was employed as supporting electrolyte. The voltammetric measurements were carried out using a stationary hanging mercury drop electrode as working electrode and a platinum electrode and an Ag|AgCl|KCl_sat electrode as auxiliary and reference electrodes, respectively. The analytical procedure was verified by analysis of standard reference materials—wholemeal BCR-CRM 189, wheat flour NIST-SRM 1567a, rice flour NIST-SRM 1568a, estuarine sediment BCR-CRM 277, river sediment BCR-CRM 320, and Montana soil with moderately elevated traces NIST-SRM 2711. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were generally below 6% whereas limits of detection for each element were below 0.069 g g^–1. In the presence of reciprocal interference the standard addition method considerably improved the resolution of the voltammetric technique, even for very high element concentration ratios. After being set up on the standard reference materials the analytical procedure was transferred and applied to commercial samples of meal and soil samples taken from sites devoted to agricultural practice. A critical comparison with graphite furnace atomic-absorption spectroscopy is also discussed. Work partially presented at Euroanalysis XIII, Salamanca, Spain, 5–10 September 2004     

Simultaneous voltammetric determination of toxic metals in sediments

Voltammetric methods are very suitable, versatile and rapid techniques for the simultaneous metal determination in complex matrices. The work, regarding the determination of As(III), Se(IV) and Mn(II), is a very interesting example of the possibility for simultaneously determining each single element in real samples in a wide range of concentration ratios. The differential pulse (DPV) measurements were carried out using a conventional three-electrode cell, while ammonia-ammonium chloride buffer (pH 9.6) was employed as the supporting electrolyte. The analytical procedure was verified by the analyses of standard reference materials: estuarine sediment BCR-CRM 277 and river sediment BCR-CRM 320. Precision and accuracy, expressed as relative S.D. and relative error, respectively, were in all cases of the order of 3-5%, while the detection limit for each element was around 10(-8) M. The standard addition technique improved the resolution of the voltammetric method, even in the case of very high element concentration ratios.     

Sequential voltammetric determination of trace metals in meals

An analytical procedure for the sequential determination of Zn(II), Cr(VI), Cu(II), Sb(III), Sn(II), Pb(II) by square wave anodic stripping voltammetry (SWASV) and Fe(III), Mn(II), Mo(VI) by square wave voltammetry (SWV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal is described.The digestion of each matrix was carried out using a concentrated HCl–HNO₃–H₂SO₄ attack mixture, employing dibasic ammonium citrate buffer solution (pH 6.9 and 8.7) as supporting electrolytes. The analytical procedure was verified by the analysis of the standard reference materials Wholemeal BCR-CRM 189, Wheat Flour NIST-SRM 1567a and Rice Flour NIST-SRM 1568a.For all the elements in the certified matrix, the precision as repeatability, expressed as relative standard deviation (s_r) was of the order of 3–5%; the accuracy, expressed as relative error (e) was generally of the order of 3–6%.In presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique.Finally, the analytical procedure was transferred and applied to commercial meals sampled on market.A critical comparison with atomic absorption spectroscopic measurements is also discussed.     

Simultaneous square-wave voltammetric determination of aspartame and cyclamate using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the simultaneous determination of aspartame and cyclamate in dietary products at a boron-doped diamond (BDD) electrode. In square-wave voltammetric (SWV) measurements, the BDD electrode was able to separate the oxidation peak potentials of aspartame and cyclamate present in binary mixtures by about 400 mV. The detection limit for aspartame in the presence of 3.0x10(-4) mol L(-1) cyclamate was 4.7x10(-7) mol L(-1), and the detection limit for cyclamate in the presence of 1.0x10(-4) mol L(-1) aspartame was 4.2x10(-6) mol L(-1). When simultaneously changing the concentration of both aspartame and cyclamate in a 0.5 mol L(-1) sulfuric acid solution, the corresponding detection limits were 3.5x10(-7) and 4.5x10(-6) mol L(-1), respectively. The relative standard deviation (R.S.D.) obtained was 1.3% for the 1.0x10(-4) mol L(-1) aspartame solution (n=5) and 1.1% for the 3.0x10(-3) mol L(-1) cyclamate solution. The proposed method was successfully applied in the determination of aspartame in several dietary products with results similar to those obtained using an HPLC method at 95% confidence level.     

Voltammetric method for ultra-trace determination of total mercury and toxic metals in vegetables. Comparison with spectroscopy

A new procedure for the determination of mercury(II), copper(II), lead(II), cadmium(II) and zinc(II) traces in food matrices by square wave anodic stripping voltammetry and standard addition method is proposed. A rapid, inexpensive and multi-analyte analytical method suitable for food safety control is provided. Comestible vegetables were chosen as samples. A two-step, sequential determination was defined, employing two working electrodes: a gold electrode (GE) for mercury(II) and copper(II), and subsequently a hanging mercury drop electrode (HMDE) for copper(II), lead(II), cadmium(II) and zinc(II). No sample pre-treatment was needed. Spinach leaves, tomato leaves and apple leaves were employed as standard reference materials to optimize and defined the analytical procedure. The new method shows good selectivity, sensitivity, detectability and accuracy. A critical comparison with spectroscopic measurements is discussed. Spinach, lettuce and tomato samples sold on the market were analysed as real samples. Lead(II) and cadmium(II) concentration exceeded the relevant legal limits.      

Voltammetric behaviour of copper(iii) and its analytical applications

Copper(II) and copper(III) complexes with periodate or tellurate ligands are electroactive at a smooth platinum electrode, giving an anodic, cathodic or cathanodic wave in the presence of alkaline hydroxide solutions containing copper(II), copper(III), or copper(II)-copper(III) species, respectively. The corresponding limiting currents are diffusion-controlled. The following analytical applications are proposed: (a) amperometric titration of copper(III) solutions; (b) voltammetric determination of copper. Results of amperometric titrations of copper(III) were similar to those by an established procedure. Voltammetry of copper(II) allows the metal to be determined down to concentrations of 1·10^-5M, even in the presence of different ions; the procedure can be applied to such heat-transfer media for nuclear reactors as sodium and potassium metals and their hydroxides.     

Determination of mercury in table salt samples by on-line medium exchange anodic stripping voltammetry

A new method for the determination of traces of total mercury by using a gold film electrode in salt samples was developed. Table salts are known to contain mercury at ultra-trace level as well as a high quantity of chloride ions that cause severe disturbance during the stripping step when gold is used as the electrode material in voltammetric measurements. The interference of high chloride content in the determination of mercury was eliminated by reducing its concentration down to 3 x 10(-3) mol L(-1) level which is optimum for the determination by using on-line medium exchange procedure immediately after the deposition step. The deposition potential applied to the electrode was maintained at 0.2 V (vs. Ag/AgCl double junction electrode) while the cell content was sucked by a pump and replaced with fresh electrolyte simultaneously. The analyte loss resulted from the air contact of the electrode was prevented by this means. The mercury ions present in the salt samples were collected at +0.2 V for 60 s, the electrolyte was replaced by 0.1 mol L(-1) HClO4 and the potential was scanned, attaining a detection limit of 0.17 microg L(-1), with R.S.D. of 1.2% (S/N=3). The recovery of the method was 94.6%. The performance and accuracy of the method was compared with that of atomic fluorescence spectrometry (AFS). Consequently, this developed method can offer a wide range of application in saline samples.