Analyst

Cite this: Analyst, 2012, 137, 424

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

View Article Online / Journal Homepage / Table of Contents for this issue

Dynamic Article Links <

www.rsc.org/analyst

PAPER

Redox magnetohydrodynamics enhancement of stripping voltammetry of lead(II), cadmium(II) and zinc(II) ions using 1,4-benzoquinone as an alternative pumping species
Ali A. Ensa,a Z. Nazaria and I. Fritsch*b
Received 4th August 2011, Accepted 30th October 2011 DOI: 10.1039/c1an15700k Differential pulse anodic stripping voltammetry (DPASV) coupled with redox-magnetohydrodynamics (MHD) is used to enhance the anodic stripping voltammetry (ASV) response using a mercury thin lm glassy carbon electrode. The sensitivity increased to at least a factor of two (at 1.2 T) and is facilitated by using 20.0 mmol L1 1,4-benzoquinone as an alternative pumping species to enhance ASV by redoxMHD. The MHD force formed by the cross-product of ion ux with magnetic eld induces solution convection during the deposition step, enhancing mass transport of the analytes to the electrode surface and increasing their preconcentrated quantity in the mercury thin lm. Therefore, larger ASV peaks and improved sensitivities are obtained, compared with analyses performed without a magnet. The inuence of pH, 1,4-benzoquinone concentration, accumulation potential, and time are also investigated. Detection limits of 0.05, 0.09 and 2.2 ng mL1 Cd(II), Pb(II) and Zn(II) were established with an accumulation time of 65 s. The method is used for the analysis of Cd(II), Pb(II) and Zn(II) in different water samples, certied reference materials, and saliva samples with satisfactory results.

Introduction
Plasma physics has been revolutionized by the discovery of magnetohydrodynamics (MHD) waves and their application to space physics and fusion research.1,2 Studies of MHD have also been reported in the literature on the effects of external magnetic elds on convection and therefore current in electrochemical systems undergoing electrolytic reactions at electrode surfaces.39 MHD is a process in which the magnetic portion of the Lorentz force can be used to propel a conductive uid, including extensive applications in pumping liquid or molten metals.1,10 MHD pumps and mixers have been recently developed for propelling redox containing electrolyte solutions in microsystems.1123 The use of MHD in the eld of microuidics has been reviewed by Qian and Bau.12 Redox species have been added to microuidic systems to avoid the problems of bubble formation and electrode dissolution.2426 The MHD force, FB (N m3), as a body force, is produced by the cross-product of ion ux j (C s1 m2) and magnetic ux density B (tesla).5 The MHD effect refers to the convection
a Department of Chemistry, Isfahan University of Technology, Isfahan, 8415683111, Iran b Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, 72701, AR, USA. E-mail: ifritsch@uark.edu This article is part of a web theme in Analyst and Analytical Methods on Future Electroanalytical Developments, highlighting important developments and novel applications. Also in this theme is work presented at the Eirelec 2011 meeting, dedicated to Professor Malcolm Smyth on the occasion of his 60th birthday.

that results from MHD. In electrochemical systems where a faradaic current is possible, the convection can affect the concentration distribution near electrodes and thereby cause changes in the limiting current under applied-potential conditions.2733 It is an enhanced mass transport-limited current in the presence of the magnetic eld that benets the anodic stripping voltammetry (ASV) measurements described herein.4,34,35 Particles and microbeads have been used to track redox-MHD convective ows.26,3638 An overview of magnetoconvective phenomena in general (which includes MHD), with a special focus on redox systems and discussion of the equations that govern the phenomena, is found in ref. 39. ASV is an electrolytic method in which an electrode is held at a reducing potential to deposit metal ions from solution at an electrode. Often, the electrode is a mercury drop or a solid conductor coated with a mercury lm. In contrast to solid electrodes, the surface of a mercury electrode is uniform, exhibits large hydrogen overpotential, and is reproducible, which make it especially useful as the electrode material of choice for ASV.40 In order to carry as much of the analyte metal ion(s) in the solution as possible to the electrode for concentration into the amalgam, convection is usually introduced, which can be accomplished by stirring or moving the electrode through solution (e.g. rotating disk electrode, hanging mercury drop electrode). After the analyte has accumulated for an adequate period of time, the potential on the electrode is changed to reoxidize the analyte and generate a current signal that is proportional to the concentration of the deposited metal.41,42 The mechanical convection
This journal is The Royal Society of Chemistry 2012

424 | Analyst, 2012, 137, 424431

View Article Online

during the preconcentration step may not be adequately efcient or suit portable analysis or that of small-volume samples in a micro-scale electrochemical cell. In contrast, MHD convection does not need moving parts to be inserted into the electrochemical cell. The effectiveness of redox-MHD convection to supply a predictable and uniform ow across the surface of the electrode during the preconcentration step has been demonstrated for the detection of the heavy metal ions Pb(II), Cd(II), and Cu(II) in conjunction with the ASV technique.4,34,35 Larger anodic stripping peaks are observed (improving sensitivities and detection limits), compared with analyses performed without a magnet. Redox-MHD has also been used to enhance convection and control the structure of metal deposits in the related eld of metal electroplating.5,7,43 In the ASV studies that used redox-MHD in the preconcentration step, the addition of high concentrations of Hg2+2 or Fe3+4,34,35 to a sample solution was necessary in low magnetic elds (<1.7 T) and with only a 1 min deposition time to achieve sufcient convection and thus signicant enhancement in the stripping signal. High concentrations of Hg2+ are undesirable due to the toxicity of Hg and the several heavy metal contaminants present in Hg(NO3)2 that lead to a nonzero faradaic background signal for those metals, increasing the detection limits. The timing of the preconcentration step also needs to be monitored carefully so that the amount of deposited Hg does not exceed the thin lm regime which occurs much more quickly with high concentrations of Hg2+ used to enhance redox-MHD pumping. Using high concentrations of Fe3+ (100 mmol L1 Fe(NO3)3) instead of Hg2+ to generate a MHD force suffers from the presence of copper as a contaminant. Fe0 may also be deposited with extreme negative potentials and contribute an additional peak to the stripping voltammogram. Another possible complication could occur in natural, sea, and industrial waters containing signicantly high concentrations of natural anthropogenic organic matter, which can make complexes with Fe3+ and contaminate the electrode by being adsorbed onto its surface. This contamination is another cause of the nonzero background signal in metal analysis by ASV. In the study herein, we have used 20.0 mmol L1 1,4-benzoquinone, instead of Hg2+ and Fe3+, as an alternative pumping reagent to enhance trace metal analysis by redox-MHD. The main advantages of 1,4-benzoquinone include its lack of toxicity compared to mercury; its lower afnity compared to Fe3+ for organic compounds in solution to make a complex; and its lower concentration compared with Fe3+ to produce a given MHD force in solution because it undergoes a two-electron transfer, instead of a one-electron transfer, and involves highly mobile H+ species in the process, presumably increasing j more for the same concentration. In addition, differential pulse anodic stripping voltammetry (DPASV) was used here instead of simple ASV to increase the analytical sensitivity and to minimize the background current of 1,4-benzoquinone to avoid rinsing before the detection step. Quantication of zinc is also new to redox-MHD ASV. To determine the effectiveness of redox-MHD convection on DPASV using 1,4-benzoquinone as the pumping species at the mercury thin lm glassy carbon electrode (MFGCE), we compared the experimental results obtained in the absence and presence of magnets. The method was evaluated by determining the analytes Cd(II), Pb(II), and Zn(II) in different water samples,
This journal is The Royal Society of Chemistry 2012

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

certied reference materials, and saliva, as well as in solutions with concentrations down to 0.05 ng mL1, which was the detection limit for Cd(II). Table 1 shows a comparison of the gures of merit of the investigated method with those reported in other publications based on stripping voltammetry.

Experimental
Chemicals and materials All chemicals used were of analytical reagent grade purchased from Merck (Darmstadt, Germany) unless otherwise stated. Deionized water (18.2 MU cm, Milli-Q systems, Millipore water) was used for preparing all solutions. Solutions of the metal ions containing Cd(II), Pb(II), and Zn(II) were prepared from nitrate salts and by appropriate dilution of the corresponding 1000 mg mL1 AA-Spectrosol standards (BDH). A 1,4-benzoquinone solution, 100.0 mmol L1, was prepared by dissolving 2.700 g of 1,4-benzoquinone in a 250 mL volumetric ask with deionized water. The universal buffer solution consisted of 0.05 mol L1 each of boric acid, phosphoric acid, and acetic acid, and where 0.1 mol L1 sodium hydroxide was added to achieve the desired pH in the range of 2.04.5. The acetate buffer solution consisted of 0.05 mol L1 each of acetic acid and sodium acetate, where 0.1 mol L1 sodium hydroxide was added to achieve the desired pH in the range of 3.54.5. Apparatus The electrochemical cell used throughout is shown in Fig. 1. It consisted of a conventional three-electrode system comprising of a MFGCE as a working electrode located in a face-downarrangement with the magnet, a Pt-wire as a counter electrode, and a Ag/AgCl (3 M KCl) reference electrode. A m-Autolab potentiostat (Eco-Chemie, The Netherlands) was employed to control the potential of the working electrode. All experiments were performed at room temperature. A combined glass electrode (conjugated with an Ag/AgCl reference electrode, Model 6.0232.100) connected to a Corning pH-meter (Model 140) was used to determine pH values of the solutions. Procedure Before each experiment, a fresh electrode surface was obtained by rst polishing the 2.0 mm diameter GCE (Autolab, EcoChemie, The Netherlands) with aluminium oxide (grain size 0.5 mm, Metrohm, Switzerland) on a micro-cloth polishing pad (Autolab, Eco-Chemie, The Netherlands). The GCE surface was then rinsed with deionized water and cleaned by sonication for 30 s. To deposit a mercury lm on the GCE, to make the MFGCE, a solution containing 50 mmol L1 KCl, 50 mol L1 HNO3 and 50 mmol L1 Hg(NO3)2 was used. The solution was stirred at 600 rpm using a stir-bar with a PAR model 305 stirrer while a potential of 0.90 V was applied to the GCE (as the working electrode) for 60 s. Quantitative measurements were performed using DPASV. The MFGCEs were placed in a round-bottom culture tube (diameter of 2.9 cm) located between the poles of a magnet. The volume of solution in the tube was 10.0 mL. All studies, except for the one that varies the magnetic ux density, were performed
Analyst, 2012, 137, 424431 | 425

View Article Online

Table 1 Comparison of results obtained using the method described herein with those reported in other publications based on stripping voltammetry Electrode Linear dynamic range Zn(II) Pb(II) Cd(II) Zn(II) Cd(II) Pb(II) Cd(II) Zn(II) Pb(II) Pb(II) Pb(II) Cd(II) Pb(II) Cu(II) Cd(II) Cd(II) Pb(II) Cu(II) Zn(II) Zn(II) Cd(II) Pb(II) Cu(II) Cd(II) Pb(II) Zn(II) 10100 mg L1 10100 mg L1 10100 mg L1 58.4646.2 mg L1 58.4646.2 mg L1 58.4646.2 mg L1 1.00110.00 mg L1 1.00110.00 mg L1 1.00130.00 mg L1 0.510 mg L1 102000 mg L1 102000 mg L1 1 105 to 5 109 mol L1 1 105 to 5 109 mol L1 1 105 to 5 109 mol L1 0.010.16 mg dm2 0.020.45 mg dm2 0.14 mg dm2 0.2810.36 mg dm2 54.3482.2 mg kg1 3.833.6 mg kg1 23.232.6 mg kg1 12.365.8 mg kg1 0.0780.0 ng mL1 0.170.0 ng mL1 4.5200.0 ng mL1 Detection limit 93 ng L1 54 ng L1 396 ng L1 28.0 mg L1 8.4 mg L1 6.6 mg L1 0.63 mg L1 0.62 mg L1 0.80 mg L1 0.15 mg L1 1.8 mg L1 2.9 mg L1 Not reported Not reported Not reported 0.25 mg L1 0.07 mg L1 2.7 mg L1 0. 5 mg L1 0.69 mg kg1 0.35 mg kg1 0.68 mg kg1 0.24 mg kg1 0.05 ng mL1 0.09 ng mL1 2.2 ng mL1 Ref. 45 46 47 48 49 50 51

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

Bismuth bulk electrode Multiwall carbon nanotube electrode Bismuth/poly(p-aminobenzene sulfonic acid) lm electrode Disposable cartridge for preconcentration and carbon as an electrode Screen-printed electrode Mercury lm deposited on wax impregnated carbon paste electrode Carbon paste electrode modied with a mercury lm

Hanging mercury drop electrode

52

Mercury thin lm-glassy carbon electrode

This work

MFGCE were carried out in 10 mL of a solution containing 0.10 mol L1 KNO3 and 20.0 mmol L1 1,4-benzoquinone in universal buffer at pH 2.0, spiked with Pb(II), Cd(II), and Zn(II) ions. The deposition step lasted 65 s at 1.10 V. The stripping step was initiated at 1.40 V and ended at 0.30 V. The instrumental parameters used in the experiments were: a modulation time of 0.002 s or an interval time of 0.1 s, a modulation amplitude of 80 mV, and a step potential of 8 mV. This is equivalent to a scan rate of 80 mV s1. Control experiments were performed in the absence of magnets (0 T).

Results and discussion

Optimization of DPASV conditions using 1,4-benzoquinone and redox-MHD The electrochemical behavior of 1,4-benzoquinone at the surface of the MFGCE was investigated using cyclic voltammetry (Fig. 2A) in the absence of magnets. The cyclic voltammogram exhibited a cathodic peak at Epc +0.09 V in the negative scan corresponding to the reduction of 1,4-benzoquinone to hydroquinone. In the positive going potential sweep, an anodic peak at Epa +0.38 V appeared that belongs to the oxidation of hydroquinone to 1,4-benzoquinone. The half-wave potential, E1/2, was +0.26 V and the peak splitting, DEp, was +0.29 V. Thus, 1,4-benzoquinone could be used as a suitable reagent to enhance deposition by redox MHD when the applied potential is more negative than +0.26 V. As shown in Fig. 2B, DPASV of 1,4-benzoquinone removes much of the cathodic signal over potentials more negative than 0.35 V. Therefore, rinsing away 1,4-benzoquinone or diluting it before the stripping step is not necessary, in contrast with the ASV approach reported previously.4,34,35
This journal is The Royal Society of Chemistry 2012

Fig. 1 The electrochemical cell with permanent magnets positioned in a metal based U-shaped structure.

with a pair of rare earth permanent magnets, separated by a 3.0 cm gap, to generate elds of 0.5 T and 1.2 T. They were diskshaped NdFeB magnets having a thickness of 1.5 cm and a diameter of 4.0 cm for the 0.5 T eld and rectangular-shaped NdFeB magnets having a thickness of 2.0 cm, a length of 4 cm, and a width of 5 cm for the 1.2 T eld. The working electrode faced downward so that its surface normal was perpendicular to the magnetic eld direction to achieve a MHD force, inducing a uid ow that is mostly parallel to the electrode surface. The tip of the reference electrode was positioned beside the working electrode with the counter electrode residing on the other side of the working electrode. The DPASV experiments with the
426 | Analyst, 2012, 137, 424431

View Article Online

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

Fig. 2 (A) Cyclic voltammetry response of 1,4-benzoquinone at the surface of a MFGCE. Conditions: KNO3, 100.0 mmol L1; universal buffer, pH 2.0; 1,4-benzoquinone, 20.0 mmol L1; 0.10 V s1. (B) DPASV of the 1,4-benzoquinone under the same conditions, but with the added parameters: deposition potential, 1.10 V; deposition time, 65 s; pulse height, 100 mV. (These results were obtained in the absence of magnets.)

The E1/2 value for 1,4-benzoquinone under these conditions is quite positive of the reduction potentials for copper, lead, and zinc ions. Thus, the 1,4-benzoquinone will not interfere by reducing the metal ions in solution. Also, there will always be a signicant cathodic current from the high concentration of 1,4benzoquinone when depositing all of these metals, contributing to a large j, and therefore a large FB and sufcient convection. The sensitivity for redox-MHD DPASV was optimized by exploring the inuence of chemical parameters and the accumulation potential and time. A concentration of 40.0 ng mL1 Pb (II) and 80.0 ng mL1 Cd(II) was used for the optimization studies. Cd(II) and Pb(II) were chosen because they are heavy metals of greater concern at low concentrations in the environment than Zn(II). It is important to control pH in these studies because the 1,4benzoquinone redox potential depends on this parameter. Therefore, the effects of different buffer types such as acetate (pH 3.54.5) and universal (pH 2.04.5) buffers on the DPASV peak currents for cadmium and lead were investigated. The results showed that DPASV peak currents for cadmium and lead ions decreased with increasing solution pH, presumably because the free metal ions (hydrated) dominate in acidic media. In addition, the loss of signal occurred more dramatically with pH in the acetate buffer solution than in the universal buffer. Thus, the universal buffer with a pH of 2.0 was selected as optimum solution conditions. The dependence of DPASV peak current on the scan rate under the optimal solution conditions was investigated in the
This journal is The Royal Society of Chemistry 2012

range of 10200 mV s1 in the presence and absence of the magnets (0.5 T). Fig. 3 shows that peak heights for cadmium (at 0.83 V) and lead (at 0.69 V) increased with increasing scan rate until about 80 mV s1. At larger scan rates, the sensitivities decreased. This behavior may be due to a decreased reversibility of 1,4-benzoquinone at higher scan rates. A scan rate of 80 mV s1 was therefore selected for quantitative studies. In addition, the results conrm that the current amplitudes for lead and cadmium are 1.7-fold with the magnets (0.5 T), compared to signals in the absence of the magnets. The inuence of accumulation potential (Eacc) on DPASV peak current for Cd(II) and Pb(II) was also investigated using the optimized solution conditions and a scan rate of 80 mV s1 in the presence and absence of the magnets (0.5 T). Fig. 4 shows that by increasing the accumulation potential from 0.60 to 1.00 V, the peak currents of Cd(II) (at 0.83 V) and Pb(II) (at 0.69 V) increased. Beyond 1.00 V, they began to level off, with the exception of peak current for Cd(II) in the presence of magnets, which continued to increase. Therefore, to provide the most sensitive response for Cd(II), 1.10 V was selected as the optimized accumulation potential for quantitation studies. (The more negative deposition potential is also more desirable for Zn (II) because of its more negative standard electrode potential, as demonstrated for real samples below.) Increasing the accumulation potential to more negative values should increase the rate of reduction of metal ions at the electrode surface. However, more negative values did not affect the peak current, presumably because of the mass transfer limit. In addition, at an accumulation potential of 1.10 V, the signal in the presence of the magnets is a factor of 1.7-times and 1.6-times that in the absence of the magnets for Pb(II) and Cd(II), respectively. Fig. 5 shows the inuence of accumulation time (20 to 200 s) on the DPASV currents for cadmium and lead ions in the presence and absence of the magnets (0.5 T). The peak currents increased for both species up to 60 s in the presence of the magnets, providing no considerable additional improvement

Fig. 3 Effect of the scan rate on the DPASV peak current for 40.0 ng mL1 Pb(II) and 80.0 ng mL1 Cd(II). (a) and (c) are for Cd(II) in the absence (open triangles) and presence (solid triangles) of magnets (0.5 T); (b) and (d) are for Pb(II) in the absence (open circles) and presence (solid circles) of magnets (0.5 T); conditions: KNO3, 100.0 mmol L1; 1,4-benzoquinone, 20.0 mmol L1; universal buffer, pH 2.0; deposition potential, 1.10 V; deposition time, 65 s; pulse height, 100 mV.

Analyst, 2012, 137, 424431 | 427

View Article Online

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

Fig. 4 Effect of deposition potential on the DPASV peak current for 40.0 ng mL1 Pb(II) and 80.0 ng mL1 Cd(II). (a) and (c) are for Cd(II) in the absence (open triangles) and presence (solid triangles) of magnets (0.5 T); (b) and (d) are for Pb(II) in the absence (open circles) and presence (solid circles) of magnets (0.5 T); conditions: KNO3, 100.0 mmol L1; 1,4benzoquinone, 20.0 mmol L1; universal buffer, pH 2.0; deposition time, 65 s; pulse height, 100 mV; scan rate, 80 mV s1.

Fig. 6 Effect of different concentrations of 1,4-benzoquinone on redoxMHD DPASV at 0.5 T of 20.0 ng mL1 Pb(II) (at 0.69 V) and 80.0 ng mL1 Cd(II) (at 0.83 V). Conditions: KNO3, 100.0 mmol L1; universal buffer, pH 2.0; deposition potential, 1.10 V; deposition time, 65 s; pulse height, 100 mV; scan rate, 80 mV s1.

beyond that time. Thus, a deposition time of 65 s was selected for subsequent experiments. At an accumulation time of 65 s the signal in the presence of the magnets was a factor of 2.3-times and 2.4-times that in the absence of the magnets for Pb(II) and Cd (II), respectively, conrming the enhancement due to MHD. The inuence of the 1,4-benzoquinone concentration from 0.1 to 40.0 mmol L1 on DPASV peak sensitivity was studied at 0.5 T. Fig. 6 shows the results for a solution containing 20.0 ng mL1 Pb(II) and 80.0 ng mL1 Cd(II). By increasing the 1,4-benzoquinone concentration from 0.1 to 20.0 mmol L1, the peak currents of Cd(II) and Pb(II) increased. Higher concentrations of 1,4benzoquinone did not signicantly affect the peak current. Increasing the concentration of the redox-MHD pumping species

increases the convection in the solution, hence increasing the rate of arrival of the metal ions from the bulk of the solution to the electrode surface. Thus, 20.0 mmol L1 of the redox-MHD pumping species was selected for subsequent studies. The effect of magnetic ux densities of 0.5 T and 1.2 T, compared to 0 T, on DPASV using solutions containing 20.0 ng mL1 Pb(II) and 150.0 ng mL1 Cd(II) was also studied. Fig. 7 shows an enhanced signal with increasing magnetic ux density under the optimized conditions. This is due to an increase in solution convection during the deposition step from the MHD force. |FB| in a given location in solution is proportional to the component of the B-eld perpendicular to the ion ux there. Leventis and Gao, who studied a similar orientation of a millimetre-sized working electrode relative to the magnet eld direction, but in a different redox solution, derived an empirical formula with a dependence of the limiting current on |B|1/3.44 If this dependence holds true during the deposition step, then the dependence of the DPASV peak current on |B| should be similar. Our results under the optimized conditions suggest a linear dependence (Fig. 7), but this is only based on two, nonzero magnetic ux densities, and thus should not be overinterpreted.

Fig. 5 Effect of the deposition time on the DPASV peak current for 40.0 ng mL1 Pb(II) and 80.0 ng mL1 Cd(II). (a) and (c) are for Cd(II) in the absence (open triangles) and presence (solid triangles) of magnets (0.5 T); (b) and (d) are for Pb(II) in the absence (open circles) and presence (solid circles) of magnets (0.5 T); conditions: KNO3, 100.0 mmol L1; 1,4-benzoquinone, 20.0 mmol L1; universal buffer, pH 2.0; deposition potential, 1.10 V; pulse height, 100 mV; scan rate, 80 mV s1.

Fig. 7 Effect of different magnetic ux densities (0.0 T, 0.5 T, and 1.2 T) on DPASV of solution containing 20.0 ng mL1 Pb(II) and 150.0 ng mL1 Cd(II). Conditions: KNO3, 100.0 mmol L1; 1,4-benzoquinone, 20.0 mmol L1; universal buffer, pH 2.0; deposition potential, 1.10 V; deposition time, 65 s; pulse height, 100 mV; scan rate, 80 mV s1.

428 | Analyst, 2012, 137, 424431

This journal is The Royal Society of Chemistry 2012

View Article Online

Figures of merit Redox-MHD DPASV at 1.2 T was used for preparation of calibration curves under the following optimum conditions: a pH of 2.0 in universal buffer, an accumulation potential of 1.10 V for 65 s, and a scan rate of 80 mV s1 with a pulse amplitude of 80 mV. Calibration curves were constructed for 0.0780.0 ng mL1 Cd(II), 4.5200.0 ng mL1 Zn(II), and 0.170.0 ng mL1 Pb(II). Typical DPASV responses of different concentrations of Cd(II), Zn(II) and Pb(II) are shown in Fig. 8, conrming that there are no interferences between those ions. Least squares analysis gave equations of |DIp| 0.1655CCd(II) mA mL ng1 + 0.1474 mA (R2 0.9947), |DIp| 0.0499CZn(II) mA mL ng1 + 0.03501 mA (R2 0.9929), and |DIp| 0.9198CPb(II) mA mL ng1 + 1.0820 mA (R2 0.9982), for Cd(II), Zn(II), and Pb(II), respectively. The results show that the system has a large linear dynamic range with low detection limits for the ions. Detection limits (CLOD 3Sb/m, where Sb is the standard deviation for 6 replicate determinations of the blank and m is the slope of the calibration curve) were 0.05, 2.2 and 0.09 ng mL1 for Cd(II), Zn(II) and Pb(II), respectively. The repeatability of the response of the method using DPASV detection for Cd(II), Zn(II) and Pb(II) was also studied. The relative standard deviations for determinations of 10.0 and 5.0 ng mL1 of Cd(II), Zn(II) and Pb(II) (n 6) were 2.8 and 1.7% for Cd(II), 4.6 and 3.3% for Zn (II), and 2.5 and 1.3% for Pb(II), respectively.

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

Real sample analysis To investigate the performance of the redox MHD-enhanced DPASV to determine an unknown concentration of Cd(II), Zn(II), and Pb(II), studies were carried out on the following samples: NIST 1640 natural water standard, river water obtained from Zayandeh-Roud river (Isfahan, Iran), lake water from Maharloo Lake (Shiraz, Iran), synthetic sea water, human saliva, spring water, and tap water. Standard addition calibration curves were used to obtain the unknown concentrations in the real samples. Amounts of 5 and 10 ng mL1 of standard analyte were added. The slopes of the best t lines from the calibration curves were then used to convert the signal to concentration for each sample containing added standard. Then, recoveries were calculated from the difference of this concentration value (with standard) minus the unknown concentration (without standard), divided by the known amount of standard added. The results are given in Table 2. They show good agreement between added or present Cd(II), Zn(II) and Pb(II) and the measured ones, as well as with analysis performed by ICP, indicating the accuracy of the method. Without further investigation, it is uncertain at this time why the standard deviations for Zn(II) analysis are higher than those for the other two metals. However, because this is true for analysis by both redox MHD-enhanced DPASV and ICP, the error is likely due to the chemistry of Zn(II) with the sample matrix and sample preparation conditions rather than to the detection method itself. Overall, the results conrm that the real samples could be analysed at the ultratrace concentration of the metal ions, with the inexpensive and simple instrumentation and procedure, and having good accuracy and precision.
Analyst, 2012, 137, 424431 | 429

Fig. 8 Redox-MHD DPASV responses of lead (0.68 V) ions, cadmium ions (0.83 V), and zinc ions (1.25 V). (A) (a) 0.5 ng mL1; (b) 2.0 ng mL1; (c) 10.0 ng mL1; (d) 20.0 ng mL1; (e) 28.0 ng mL1; (f) 33.0 ng mL1; (g) 38.0 ng mL1; (h) 50.0 ng mL1; and (i) 58.0 ng mL1 Pb (II) at xed concentrations of 40.0 ng mL1 Cd(II) and 25.0 ng mL1 Zn(II). (B): (a) 1.0 ng mL1; (b) 10.0 ng mL1; (c) 20.0 ng mL1; (d) 30.0 ng mL1; (e) 40.0 ng mL1; (f) 50.0 ng mL1; (g) 58.0 ng mL1; (h) 62.0 ng mL1; and (i) 70.0 ng mL1 Cd(II) at xed concentrations of 7.0 ng mL1 Pb(II) and 25.0 ng mL1 Zn(II). (C): (a) 6.0 ng mL1; (b) 10.0 ng mL1; (c) 25.0 ng mL1; (d) 30.0 ng mL1; (e) 35.0 ng mL1; (f) 50.0 ng mL1; (g) 65.0 ng mL1; (h) 70.0 ng mL1; and (i) 85.0 ng mL1 Zn(II) at xed concentrations of 40.0 ng mL1 Cd(II) and 7.0 ng mL1 Pb(II). Conditions: KNO3, 100.0 mmol L1; universal buffer, pH 2.0; deposition potential, 1.10 V; deposition time, 65 s; pulse height, 100 mV; scan rate, 80 mV s1; 1.2 T.

This journal is The Royal Society of Chemistry 2012

View Article Online

Table 2 Determination of Cd(II), Zn(II) and Pb(II) in water samples Added/ng mL1 Sample Cd 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 Zn 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 Pb 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 5.0 10.0 Found/ng mL1 Cd 0.30(0.01) 5.8(0.4) 10.5(0.7) 1.2(0.2) 6.8(0.7) 11.6(1.1) 0.30(0.01) 4.8(0.3) 10.8(1.1) 1.5(0.3) 6.4(0.5) 11.6(0.8) 6.6(0.5) 11.7(0.6) 16.7(1.2) 9.5(0.6) 15.1(0.7) 20.3(1.4) 21.5(1.5) Zn 36.4(2.2) 41.8(2.3) 46.8(2.9) 186.4(3.5) 191.3(3.3) 195.8(4.8) 47.5(1.1) 52.3(1.8) 57.6(1.6) 143.0(2.8) 148.8(3.9) 152.8(4.1) 200.4(3.5) 206.8(3.4) 210.8(3.7) 45.0(4.5) 50.8(5.2) 55.0(6.7) 54.7 (1.7) Pb 4.5(0.8) 10.2(1.5) 15.4(1.7) 9.5(0.7) 14.3(0.8) 20.2(1.0) 2.2(1.21) 7.7(0.58) 12.3(0.95) 9.3(0.8) 14.8(1.0) 19.7(1.1) 15.5(1.1) 20.8(1.3) 26.1(1.2) 45.8(1.3) 50.4(1.4) 55.3(1.3) 26.7(1.0) Recovery (%) Cd 110 102 112 104 90 105 98 101 102 101 112 108 Zn 108 104 98 94 96 101 116 98 128 104 116 100 Pb 114 109 96 107 110 101 110 104 106 106 92 95 Found by ICP methodb/ng mL1 Cd 0.3(0.1) 5.3(0.8) 1.0(0.2) 1.3(0.4) 6.9(0.8) 8.9(0.8) Zn 32.8(2.7) 41.8(3.5) 195.2(8.1) 150.0(5.1) 211.1(8.3) 45.6(5.5) Pb 4.9(1.0) 9.9(1.1) 10.1(0.9) 9.0(1.0) 14.2(2.1) 41.3(1.8)

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

Tap water (Isfahan, Iran) Spring water Human saliva Zayandeh-Roud River (Isfahan, Iran) Synthesized sea watera Lake Maharloo water (Shiraz, Iran) NIST 1640c

a Containing 5.5 and 16.0 ng mL1 Cd(II) and Pb(II), respectively. b Analysis was done after a 100-fold preconcentration of the sample by evaporation. Standard deviations were obtained from triplicate analyses (N 3). c Cd(II), Zn(II) and Pb(II) was 22.79 0.96, 53.2 1.1 and 27.89 0.14 ng mL1, respectively.

Conclusions
Redox-MHD with a high concentration of the pumping species 1,4-benzoquinone was used for the rst time in solutions containing trace concentrations of analyte metals to produce convection and therefore enhance deposition for a stripping analysis. A signicant advantage of 1,4-benzoquinone over other pumping species used in past redox-MHD stripping studies is that there is no need to remove it or dilute it before the detection step, greatly simplifying the procedure. Redox-MHD with 1,4-benzoquinone was shown here to enhance DPASV signals of Cd(II), Pb(II) and Zn(II) ions for solutions containing 0.5 to 85 ng mL1 of those ions by inducing convection during the preconcentration step. Detection limits as low as 0.05 ng mL1 Cd(II) were measured with an accumulation time of only 65 s. This method is more sensitive and has better limits of detection (from 0.05 to 2.2 ng mL1) than those found in previously published papers4553 where DPASV was used to determine these ions and a stirrer and stir bar provided solution convection. In addition, the detection limit for Cd(II) here is improved by a factor of 30 from that reported previously for redox-MHD, which had 1.5 times the magnetic ux density (1.77 T) for the same deposition period (60 s) using ASV and a Fe3+ pumping uid (at 5 times the concentration, 100 mmol L1).34 More studies are needed to determine the reasons for the dramatically enhanced detection limits over the earlier redoxMHD studies. Possible explanations include the use of DPASV instead of ASV, avoiding the rinsing/dilution step before stripping, and the use of a pumping species that undergoes a 2electron transfer that is associated with high ion ux of H+. Nevertheless, the results herein strongly encourage the use of redox-MHD to achieve convection in portable trace metal stripping analysis devices.
430 | Analyst, 2012, 137, 424431

Acknowledgements
The authors are thankful to Isfahan University of Technology Research Council (Iran) and the National Science Foundation (Grant CHE-0719097, USA) for support of this work.

References
1 P. A. Davidson, An Introduction to Magnetohydrodynamics, Cambridge University Press, New York, 2001. 2 J. P. H. Goedbloed and S. Poedts, Principles of Magnetohydrodynamics: with Applications to Laboratory and Astrophysical Plasmas, Cambridge University Press, 2004. 3 O. Aaboubi, J. P. Chopart, J. Douglade, A. Olivier, C. Gabrielli and B. Tribollet, Magnetic eld effects on mass transport, J. Electrochem. Soc., 1990, 6, 17961804. 4 E. A. Clark and I. Fritsch, Anodic stripping voltammetry enhancement by redox magnetohydrodynamics, Anal. Chem., 2004, 76, 24152418. 5 T. Z. Fahidy, Magnetoelectrolysis, J. Appl. Electrochem., 1983, 13, 553563. 6 S. Fujiwara, Y. Umezawa and T. Kugo, Effect of static magnetic eld on direct current polarography, Anal. Chem., 1968, 40, 2186 2190. 7 R. A. Tacken and L. J. J. Janssen, Applications of magnetoelectrolysis, J. Appl. Electrochem., 1995, 25, 15. 8 J. L. Anderson, L. A. Coury, Jr and J. Leddy, Dynamic electrochemistry: methodology and application, Anal. Chem., 2000, 72, 44974520. 9 A. Alemany and J.-P. Chopart, in Magnetohydrodynamics: Historical Evolution and Trends (Fluid Mechanics and its Applications), ed. S. Molokov, Springer, 2007, vol. 80, pp. 391407. 10 R. S. Baker and M. J. Tessier, Handbook of Electromagnetic Pump Technology, Elsevier Science Publishing, Co., New York, 1987. 11 J. Jang and S. S. Lee, Theoretical and experimental study of MHD (magnetohydrodynamic) micropump, Sens. Actuators, A, 2000, 80, 8489. 12 S. Qian and H. H. Haim, Magneto-hydrodynamics based microuidics, Mech. Res. Commun., 2009, 36, 1021.

This journal is The Royal Society of Chemistry 2012

View Article Online

13 H. H. Bau, J. Zhu, S. Qian and Y. Xiang, A magnetohydrodynamically controlled uidic network, Sens. Actuators, B, 2003, 88, 205216. 14 J. Zhong, M. Yi and H. H. Bau, Mageto hydrodynamic (MHD) pump fabricated with ceramic tapes, Sens. Actuators, A, 2002, 96, 5966. 15 J. C. T. Eijkel, C. Dalton, C. J. Hayden, J. P. H. Burt and A. Manz, A circular ac magnetohydrodynamic micropump for chromatographic applications, Sens. Actuators, B, 2003, 92, 215221. 16 A. Homsy, V. Linder, F. Lucklum and N. F. de Rooij, Magnetohydrodynamic pumping in nuclear magnetic resonance environments, Sens. Actuators, B, 2007, 123, 636646. 17 A. V. Lemoff and A. P. Lee, An AC magnetohydrodynamic micropump, Sens. Actuators, B, 2000, 63, 178185. 18 A. V. Lemoff and A. P. Lee, An AC Magnetohydrodynamic microuidic switch for micro total analysis systems, Biomed. Microdevices, 2003, 5, 5560. 19 B. Nguyen and S. K. Kassegne, High-current density DC magenetohydrodynamics micropump with bubble isolation and release system, Microuid. Nanouid., 2008, 5, 383393. 20 S. Qian and H. H. Bau, Magnetohydrodynamic ow of RedOx electrolyte, Phys. Fluids, 2005, 17, 067105. 21 L. Wang, L. Flanagan and A. P. Lee, Side-wall vertical electrodes for lateral eld microuidic applications, J. Microelectromech. Syst., 2007, 16, 454461. 22 J. West, J. P. Gleeson, J. Alderman, J. K. Collins and H. Berney, Structuring laminar ows using annular magnetohydrodynamic actuation, Sens. Actuators, B, 2003, 96, 190199. 23 J. West, B. Karamata, B. Lillis, J. P. Gleeson, J. Alderman, J. K. Collins, W. Lane, A. Mathewson and H. Berney, Application of magnetohydrodynamic actuation to continuous ow chemistry, Lab Chip, 2002, 2, 224230. 24 Z. P. Aguilar, P. U. Arumugam and I. Fritsch, Study of magnetohydrodynamic driven ow through LTCC channel with self-contained electrodes, J. Electroanal. Chem., 2006, 591, 201209. 25 P. U. Arumugam, E. S. Fakunle, E. C. Anderson, S. R. Evans, K. G. King, Z. P. Aguilar, C. S. Carter and I. Fritsch, Redox magnetohydrodynamics in a microuidic channel: characterization and pumping, J. Electrochem. Soc., 2006, E185E194. 26 M. C. Weston, C. K. Nash and I. Fritsch, Redoxmagnetohydrodynamic microuidics without channels and compatible with electrochemical detection under immunoassay conditions, Anal. Chem., 2010, 82, 70687072. 27 K. M. Grant, J. W. Hemmert and H. S. White, Magnetic eld driven convective transport at inlaid disk microelectrods. The dependence of ow patterns on electrode radius, J. Electroanal. Chem., 2001, 500, 9599. 28 J. Lee, X. Gao, L. D. A. Hardy and H. S. White, Inuence of magnetic elds on the voltammetric response of microelectrodes in highly concentrated organic redox solutions, J. Electrochem. Soc., 1995, 142, L90L92. 29 J. Lee, S. R. Ragsdale, X. Gao and H. S. White, Magnetic eld control of the potential distribution and current at microdisk electrodes, J. Electroanal. Chem., 1997, 422, 169177. 30 S. R. Ragsdale, J. Lee, X. Gao and H. S. White, Magnetic eld effects in electrochemistry. Voltammetric reduction of acetophenone at microdisk electrodes, J. Phys. Chem., 1996, 100, 59135922. 31 S. R. Ragsdale, J. Lee and H. S. White, Analysis of the magnetic force generated at a hemispherical microelectrode, Anal. Chem., 1997, 69, 20702076. 32 S. R. Ragsdale and H. S. White, Analysis of voltammetric currents in concentrated organic redox solutions using the cullinanvignes equation and activity-corrected mutual diffusion coefcients, J. Electroanal. Chem., 1997, 432, 199203. 33 S. R. Ragsdale and H. S. White, Imaging microscopic magnetohydrodynamic ows, Anal. Chem., 1999, 71, 19231927. 34 E. C. Anderson and I. Fritsch, Factors inuencing redox magnetohydrodynamic-induced convection for enhancement of stripping analysis, Anal. Chem., 2006, 78, 37453751. 35 M. C. Weston, E. C. Anderson, P. U. Arumugam, P. Yoga Narasimhan and I. Fritsch, Redox magnetohydrodynamic enhancement of stripping voltammetry: toward portable analysis using disposable electrodes, permanent magnets, and small volumes, Analyst, 2006, 131, 13221331. E. C. Anderson, M. C. Weston and I. Fritsch, Investigations of redox magnetohydrodynamic uid ow at microelectrode arrays using microbeads, Anal. Chem., 2010, 82, 26432651. C. Cierpka, R. Segura, R. Hain and C. J. K ahler, A simple single camera 3C3D velocity measurement technique without errors due to depth of correlation and spatial averaging for microuidics, Meas. Sci. Technol., 2010, 21, 045401. C. Cierpka, T. Weier, G. Gerbeth, M. Uhlemann and K. Eckert, Copper deposition and dissolution in seemingly parallel electric and magnetic elds: Lorentz force distributions and ow congurations, J. Solid State Electrochem., 2007, 11, 687701. M. C. Weston, M. D. Gerner and I. Fritsch, Magnetic elds for uid motion, Anal. Chem., 2010, 82, 34113418. S. P. Kounaves and M. A. Nolan, Microfabricated array of iridium microdisks as a substrate for direct determination of Cu2+ or Hg2+ using square-wave anodic stripping voltammetry, Anal. Chem., 1999, 71, 35673573. A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, John Wiley & Sons, Inc., New York, 2001. J. Wang, Analytical Electrochemistry, Wiley-VCH, New York, 2000. G. Hinds, F. E. Spada, J. M. D. Coey, T. R. N Mh och ain and M. E. G. Lyons, Magnetic eld effects on copper electrolysis, J. Phys. Chem., 2001, 105, 94879502. N. Leventis and X. Gao, Steady-state voltammetry with stationary disk millielectrodes in magnetic elds: nonlinear dependence of the mass-transfer limited current on the electron balance of the faradaic process, J. Phys. Chem. B, 1999, 103, 58325840. K. C. Armstrong, C. E. Tatum, R. N. Dansby-Sparks, J. Q. Chambers and Z. L. Xue, Individual and simultaneous determination of lead, cadmium, and zinc by anodic stripping voltammetry at a bismuth bulk electrode, Talanta, 2010, 82, 675 680. C. R. T. Tarley, V. S. Santos, B. E. L. Ba^ eta, A. C. Pereira and L. T. Kubota, Simultaneous determination of zinc, cadmium and lead in environmental water samples by potentiometric stripping analysis (PSA) using multiwalled carbon nanotube electrode, J. Hazard. Mater., 2009, 169, 256262. Y. Wu, N. B. Li and H. Q. Luo, Simultaneous measurement of Pb, Cd and Zn using differential pulse anodic stripping voltammetry at a bismuth/poly(p-aminobenzene sulfonic acid) lm electrode, Sens. Actuators, B, 2008, 133, 677681. H. Mongi, A. Kida, N. Uchida, K. Iwasa and S. Nakano, Determination of lead by stripping voltammetry with a disposable cartridge for quality control of municipal solid waste molten slag, Microchem. J., 2011, 97, 220224.  and A. Merkoci, Sensitive ell, G. Aragay, C. Font R. Gu as, E. Antico and stable monitoring of lead and cadmium in seawater using screenprinted electrode and electrochemical stripping analysis, Anal. Chim. Acta, 2008, 627, 219224. B. S. Sherigara, Y. Shivaraj, R. J. Mascarenhas and A. K. Satpati, Simultaneous determination of lead, copper and cadmium onto mercury lm supported on wax impregnated carbon paste electrode: assessment of quantication procedures by anodic stripping voltammetry, Electrochim. Acta, 2007, 52, 31373142. J. Jakmunee and J. Junsomboon, Determination of cadmium, lead, copper and zinc in the acetic acid extract of glazed ceramic surfaces by anodic stripping voltammetric method, Talanta, 2008, 77, 172 175. S. A. Mahesar, S. T. H. Sherazi, A. Niaz, M. I. Bhanger, S. Uddin and A. Rauf, Simultaneous assessment of zinc, cadmium, lead and copper in poultry feeds by differential pulse anodic stripping voltammetry, Food Chem. Toxicol., 2010, 48, 23572360. A. A. Ensa, Z. Nazari and I. Fritsch, Highly sensitive differential pulse voltammetric determination of Cd, Zn, and Pb ions in water samples using stable carbon-based mercury thin-lm electrode, Electroanalysis, 2010, 22, 25512557.

36 37

Published on 24 November 2011. Downloaded by Empresa Brasileira de Pesquisa Agropecuaria on 06/06/2013 19:31:01.

38

39 40

41 42 43 44

45

46

47

48

49

50

51

52

53

This journal is The Royal Society of Chemistry 2012

Analyst, 2012, 137, 424431 | 431