Sensors and Actuators B 186 (2013) 451–460

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Sensors and Actuators B: Chemical

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Simultaneous electrochemical determination of heavy metals using a

triphenylphosphine/MWCNTs composite carbon ionic liquid electrode
Hasan Bagheri a,∗ , Abbas Afkhami b , Hosein Khoshsafar b ,
Mosayeb Rezaei b , Ali Shirzadmehr b
a
Department of Chemistry, Takestan Branch, Islamic Azad University, Takestan, Iran
b
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: A constructed triphenylphosphine-modified carbon nanotube composite with a room temperature ionic
Received 2 March 2013 liquid as pasting binder was employed as a novel electrode for sensitive and simultaneous determina-
Received in revised form 31 May 2013 tion of Cd2+ , Pb2+ and Hg2+ . The morphology and properties of electrodes surface were characterized by
Accepted 15 June 2013
scanning electron microscopy (SEM) and electrochemical impedance spectroscopy. The electrochemical
Available online xxx
response characteristics of the modified electrode toward the analytes ions were investigated by square-
wave anodic stripping voltammetry (SWASV). The responses of modified electrode for Cd2+ , Pb2+ and
Keywords:
Hg2+ were found to be improved significantly in comparison with those obtained using a conventional
Simultaneous determination
Heavy metals
carbon paste electrode. The experimental conditions for simultaneous determination of these ions have
Square wave voltammetry been established. Relative standard deviations to detect the Cd2+ , Pb2+ and Hg2+ in ternary mixtures were
Modified carbon paste electrodes less than 3.0% and they can be determined in the ranges of 0.1–150.0 nM. Under optimal conditions the
Multi walled carbon nanotube limits of detection were 6.0 × 10−5 , 9.2 × 10−5 and 7.4 × 10−5 ␮M for Pb2+ , Hg2+ and Cd2+ with a 75 s pre-
concentration, respectively. The method was applied to determine the cadmium, lead and mercury in
soil, gasoline, fish, tap water and waste water samples.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction developed for environmental monitoring, depending on the nature

of the analyte, the characteristics of the sample matrix and required
Heavy metals are not biodegradable and therefore they remain sensitivity or selectivity. From a chemistry perspective, insufficient
in ecological systems and in the food chain indefinitely, exposing long-term stability of the sensing interface, active interferences in
top-level predators to very high levels of pollution. Elevated levels the sample, drift over time, difficult and/or repetitive calibration,
of heavy metals in natural environmental samples may have a detri- biofouling due to the environmental conditions in joint with the
mental effect on both human health and the environment [1,2]. typical need of low detection limits are major issues which have
Apart from the direct impact on health or environmental problems, not entirely solved [7–9]. Thus, high level of maintenance, e.g., need
water or soil contamination can cause considerable economic and recalibrate and rejuvenate the sensors, precludes their use in long
financial damage, so there is a need for novel instruments capable term applications [10–12].
of real-time and in situ detection of heavy metals [3,5]. The atomic Among all of the electrochemical methods, stripping voltam-
spectrometric methods are expensive and not suitable for in situ metric analysis provides a powerful tool for the determination of
analysis due to the ponderous and complicated instruments. On metal ions, which possess high-sensitivity and can simultaneously
the contrary, the electrochemical methods as an alternative of these analyze several heavy metal ions [13]. The use of the chemical mod-
spectroscopic techniques, have been accepted as the efficient meth- ified electrodes greatly improves the efficiency of accumulating
ods to detect heavy metal ions due to their excellent sensitivity, target analytes without interferences compared with the conven-
short analysis time, portability, and low cost [5,6]. tional voltammetric techniques [14].
Having access to robust, sensitive, selective and low-cost chem- The key point to obtain a good and reliable electrochemical sen-
ical sensors is becoming of paramount importance in a growing sor is the kind of materials that constitute the detection platform.
number of situations. Different electrochemical devices have been In this field, the synergy between electrochemical sensors technol-
ogy and nanomaterials is expecting to bring interesting advantages
in the field of new electrochemical transducing platforms beside
∗ Corresponding author. Tel.: +98 282 5270130; fax: +98 282 5270130. their use as electrochemical labels or tags for signal enhancement
E-mail addresses: [email protected], [email protected] (H. Bagheri). [15]. Sensors based on nanostructured materials take advantages of

0925-4005/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.06.051
452 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460

the increased electrode surface area, increased mass-transport rate, donor atoms [13]. Cd2+ , Hg2+ and Pb2+ ions are classified as the soft
and fast electron transfer compared to electrodes based on bulk acids and based on HSAB theory they prefer to bond with soft bases.
materials [15,16]. In addition to novel properties, nanomaterials PPh3 is a soft Lewis base and coordinate to the analyte ions using
open up new approaches to fabricate the electrodes cost effectively the lone pair on phosphorus and show relatively low ␲-acidity. The
by minimizing the needed materials and waste generation [17]. electronic flexibility of PPh3 is the reason it forms form stable com-
The unique properties of carbon nanotube, as a “magic” material, plexes with soft heavy metals of high polarizability such as Cd2+ ,
make them extremely attractive for fabricating chemical sensors, Hg2+ and Pb2+ ions. Therefore, it was successfully used as a com-
in general, and electrochemical ones, in particular. Multiwalled plexing agent for the selective voltammetric determination of Cd2+ ,
carbon nanotubes (MWCNTs) have been shown to impart good Hg2+ and Pb2+ ions at a carbon paste electrode (CPE) modified with
responses and minimization of surface fouling in electrochemi- MWCNTs and IL. Such properties caused obtaining low detection
cal devices. They have attracted considerable interest for use as limits in the voltammetric determinations with modified CPE as a
an electrode component due to their excellent properties, such as working electrode. The created selectivity in this procedure makes
increased electrode surface area, fast electron transfer rate, signif- the electrode very suitable for the detection of trace amounts of
icant mechanical strength and good chemical stability. They can target analytes in various real samples.
act simultaneously as adsorbent/preconcentrator agent and trans-
ducer platform [15]. It is due to large apparent surface areas of
MWCNTs and their electrocatalytic nature attributed to the activ- 2. Experimental
ity of the edge-plane-like graphite sites at their ends [15,18]. Also,
carbon nanotubes paste electrodes show several advantages, such 2.1. Apparatus and chemicals
as increased current because of increased mass transport at the
working electrode boundary, decreased detection limit, increased In order to prevent metals contamination, laboratory glassware
signal-to-noise ratio since noise only depends on the active area of were kept overnight in a 10% (v/v) nitric acid solution prepared
the sensor, and effective incorporation into devices. Its proof is the by dilution of concentrated nitric acid (65%, Merck, Germany).
great number of publications referred to this field [18]. All chemicals were of analytical grade and used without any
Recently, as a new “green” media, room temperature ionic liq- further purification. Unless otherwise stated, all the solutions
uids (RTILs) have emerged as a frontier and novel area of research were prepared with doubly distilled water (DDW). 1-butyl-1-
because of their excellent chemical and physical properties such as methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (IL) and
high chemical and thermal stability, ionic nature, good extraction chloride and nitrate salts of the cations were purchased from Merck.
ability, ion-exchange properties, low equilibrium vapour pressure, Graphite powder (size <30 ␮m, spectral pure) and paraffin oil were
high conductivity and wide electrochemical windows [19]. Also, obtained from Merck. Acetate buffer solutions of 0.1 M for differ-
RTILs have been proposed as efficient pasting binders in place ent pH were prepared by mixing stock solutions of 0.1 M NaAc
of non-conductive organic binders for the preparation of carbon and HAc. Phosphate buffer solutions (PBS) of 0.1 M were prepared
composite electrodes [5,12,16,19,20]. These ionic liquid modified by mixing stock solutions of 0.1 M H3 PO4 , KH2 PO4 , K2 HPO4 , and
carbon electrodes show some advantages over traditional CPEs, NaOH. Britton-Robinson (B-R) universal buffers (pH 2–10) were
such as high conductivity and sensitivity, fast electron transfer and prepared in DDW and were tested as supporting electrolytes. Work-
good antifouling ability for electroanalysis. Moreover, the combi- ing stock solutions of metal cations (1 mg L−1 ) were prepared from
nation of such materials with specific ligands can provide excellent 1000 mg L−1 atomic absorption standard solutions. All standard and
electrochemical platforms for heavy metals analysis due to the stock solutions were diluted as required with DDW.
combination of the enlarged active surface area, strong adsorptive Voltammetric measurements were performed using an Autolab
capability of the nanomaterial and the specific complexing ability electrochemical system (302 N, Utrecht, Netherlands). The electro-
of the ligands [21]. chemical cell was assembled with a conventional three-electrode
Reliable simultaneous determination of more than one metal system: an Ag/AgCl/KCl (3 M) reference electrode (Metrohm) and a
using stripping analysis is difficult due to the possibility of over- platinum wire as counter electrode. A modified or unmodified car-
lapping peaks, which can occur in the relatively narrow potential bon paste electrode was used as working electrode. A multimeter
range where metals are reduced or oxidized. One approach to elimi- was used for ohmic resistance measurements.
nate the problem of interferences is to employ chemically modified The micrographs of the modified electrodes were investigated
electrodes (CME). A major advantage of using the CME is that it by SEM (SEM-EDX, XL30, Philips Netherland). The inductively cou-
can detain a wider adjustable preconcentration without interfer- pled plasma-optical emission spectrometer (ICP-OES) was used the
ences compared with the conventional voltammetric techniques. Jobin-Yvon Emission (JY138 ultrace, France). Details of operating
When the experimental condition is optimized, the method with conditions for the determination of cations were as manufacture
a CME has the least interference by other species in the sample. manual. pH adjustments were carried out by a Metrohm model
The operation mechanism of such chemically modified electrodes 713 (Herisau, Switzerland) pH-Meter.
depends on the properties of the modifier used that affect its selec-
tivity toward the target species. Triphenyl phosphine (PPh3 ) binds
well to most transition metals, especially those in the middle and 2.2. Pretreatment of multi-walled carbon nanotubes
late transition metals of groups. As far as we know, the works avail-
able in the literature report the simultaneous determination of two In order to remove the probable amorphous carbon, graphitic
metal ions, and only few studies were devoted to the simultaneous nanoparticles, catalytic impurities and/or to improve the electron
and selective determination of three metal ions (Cd2+ , Pb2+ and transfer properties and/or to allow further functionalization, a pro-
Hg2+ ) in different real samples (Table 1). The aim of this paper is to cedure similar to a previous report was used [22]. Briefly, a 500 mg
combine mentioned unique properties of MWCNTs and ionic liquid of the MWCNTs were heated in an oven with 400 ◦ C in nitrogen
with the specific complexing ability of PPh3 to fabricate an elec- atmosphere for 2 h. Then MWCNTs were dispersed in 50 mL of 6.0 M
trochemical sensor toward heavy metal ions with high sensitivity HCl for 2 h under ultrasonic agitation under the nitrogen atmo-
and selectivity. According to the theory of hard and soft acids and sphere; filtered on a Wattman 42 filter paper and washed with
bases (HSAB) defined by Pearson, metal ions will have a preference DDW until the pH of the solution was neutral. These MWCNTs were
for complexing with ligands that have more or less electronegative dried under the IR lamp.
 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460 453

Table 1
Comparison of some figures of merit of the recently suggested electrodes for the determination of some analyte ions.

Electrode Method Linear range (␮M) DL (␮M) Refs.

Pb(II) Hg(II) Cd(II) Pb(II) Hg(II) Cd(II)

Bismuth film/IL/CPE SWASV 4.8 × 10−3 to 0.48 N.M.a 8.9 × 10−3 to 0.89 5.0 × 10−4 N.M. 8.9 × 10−4 [7]
Schiff base/MWCNT/ SWASV 2.0 × 10−3 to 0.7 2.0 × 10−3 to 0.7 N.M. 6.00 × 10−4 9.00 × 10−4 N.M. [30]
CPE
N-BDMP/CPE SWASV N.M. 4.9 × 10−2 to 9.96 8.8 × 10−2 to 17.78 N.M. 4.1 × 10−2 5.9 × 10−2 [33]
Antimony SWASV 4.8 × 10−2 to 0.48 N.M. 8.8 × 10−2 to 0.88 3.3 × 10−3 N.M. 8.9 × 10−3 [34]
trioxideb /CPE
CNT tower electrodes OSWSV 0.5–3.0 N.M. 1.0-4.0 1.2 × 10−2 N.M. 2.5 × 10−2 [35]
SBA-15c /CPE DPASV 0.3–7 N.M. 2.0–10.0 0.04 N.M. 0.4 [36]
Montmorillonite- SWASV 4.8 × 10−3 to 0.11 N.M. 8 × 10−3 to 0.21 9.6 × 10−4 N.M. 3.1 × 10−3 [37]
bismuth-carbon
electrodes
Bismuth–Nafion- SWASV 9.6 × 10−3 to 5.7 × 10−2 N.M. 1.7 × 10−2 to 0.1 3.3 × 10−4 N.M. 4.1 × 10−3 [38]
medical stone doped
disposable electrode
Bismuth bulk electrode SWASV 4.8 × 10−2 to 0.48 N.M. 8.9 × 10−2 to 0.88 4.5 × 10−4 N.M. 04.8 × 10−4 [39]
EDTA bonded SWASV 7.5 × 10−4 to 0.1 7.5 × 10−4 to 0.1 N.M. 6.0 × 10−4 5.0 × 10−4 N.M. [40]
conducting polymer
modified electrode
SBA-15/IL/CPE DPASV 0.40–90.00 0.08–50.00 0.6–30.0 4.00 × 10−2 1.00 × 10−2 0.08 [41]
PPh3 /MWCNTs/IL/CPE SWASV 1 × 10−4 to 0.15 1 × 10−4 to 0.15 1 × 10−4 to 0.15 6.0 × 10−5 9.2 × 10−5 7.4 × 10−5 This work
a
Not measured.
b
Nitro benzoyl diphenylmethylenphosphorane.
c
Nanostructured silica organofunctionalised with 2-benzothiazolethiol.

2.3. Electrodes preparation a standard 0.45 ␮m filter. Prior to the test, the pH of the samples
was adjusted to 3.0 by using 0.1 M HCl solution.
The carbon paste mixture was prepared by thoroughly hand The soil sample was collected from some regions with cultivated
mixing of spectroscopic graphite powder with appropriate amount lands (Hamedan), which are near industrial areas. The treatment of
of binder (paraffin oil or IL) in a mortar using a pestle (75:25, samples was performed according to the reports [7]. First, 1.0 g of
w/w%). A portion of the composite mixture was packed firmly a soil sample was heated in an oven at 80 ◦ C for one hour. Then, the
piston-driven carbon paste electrode holder. In order to prepare soil sample was placed in an extraction tube with 40 mL of 0.1 M
carbon nanotube paste electrode, the treated MWCNT (10% w/w) acetic acid. The mixed sample was sonicated for 1 h. Then the mix-
were mixed with fine graphite powder in an appropriate volume ture was centrifuged for phase separation and the aqueous phase
of dichloromethane (for more homogeneity of the electrode com- was filtered with filters of 0.22 ␮m pore size. After these processes,
posite components leading to an increase in the reproducibility the free metal ions in the soil samples were extracted. Prior to the
after each electrode surface polishing). The mixture was stirred by test, the pH of the obtained extract solutions was adjusted to 3.0
a magnetic stirrer till the solvent evaporated completely. The pre- by using 0.1 M NaOH solution.
pared modified composite was then air dried for 24 h and used in The proposed method was applied to determine of cadmium,
the same way as the case of the unmodified electrode. To prepare lead and mercury in dried fish samples. Dried fish was purchased
the PPh3 modified electrode a 15% w/w portion of PPh3 mixed from local fish market. 1.0 g of dried fish sample was placed in a
with carbon nanotube paste electrode and resulted composite was round-bottom flask and 10 mL of HNO3 (70%), 10 mL of H2 SO4 (98%),
dispersed in dichloromethane. The homogenized composite was 10 mL of K2 S2 O8 (5%) and 8 mL of KMnO4 (5%) were added and
stirred by a magnetic stirrer till the solvent evaporated completely. refluxed at 250 ◦ C for about 2 h. The digested fish sample was cooled
Then, the prepared modified composite was air dried for 24 h. to room temperature [23]. Appropriate amounts of 2 M of NaOH
Then IL was added to prepared mixtures and they were mixed solution was added to neutralize the excess of HNO3 and diluted to
until uniform pastes were obtained. Each paste was transferred 1000 mL in a volumetric flask. An aliquot of the solution was treated
into the piston-driven carbon paste electrode holder. The paste under recommended procedure.
was carefully packed into the body tip to avoid possible air gaps, The gasoline samples were collected in September 2012 in dif-
which often enhance the electrode resistance. When needed, the ferent station within the city of Hamedan, Iran. The samples were
surface of carbon paste was mechanically renewed by extruding ca. digested in a mixture of HNO3 and H2 O2 with the assistance of
0.5 mm of carbon paste out of the electrode holder and smoothed microwave heating. Typically, an aliquot of 500 ␮L of gasoline sam-
with a filter paper. Usually, this simple operation was made before ple (375 mg) was mixed with 5 mL of concentrated HNO3 and 2 mL
starting a new set of experiments. This composite has remarkable of H2 O2 . The microwave power was ramped to 500 W in 2 min, and
advantages, such as high compactness and mechanical stability, kept it for 15 min. Then the power was increased to 1000 W in 2 min,
low electrical resistance and renewal characteristics by simple pol- and held it for 20 min. In the heating processes, the ventilation of
ishing. The prepared CPEs were then immersed in the supporting the oven was set at level 1. After that, the microwave was shut
electrolyte placed in the electrolysis cell and several sweeps were down, the mixture was kept in the oven for 5 min with a ventila-
applied until a low background current was achieved. tion set at level 3. After digestion, the solution was diluted to 25 mL
with DDW, which was used for electrochemical measurement. Two
duplicated digestions were performed for each sample [24].
2.4. Samples preparation
2.5. Analytical procedure
Water samples (waste and tap water) have been utilized to eval-
uate the applicability of the proposed electrode for monitoring the The analysis of Cd2+ , Pb2+ and Hg2+ ions using SWV was carried
target ions in real samples. The water samples were filtered through out in a 20.0 mL aliquot using the following steps; first, potential
454 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460

1.0 V for 30 s was applied before each measurement to ensure disso- formed on the graphite particles even with the addition of a small
lution of remaining deposits; after that, the working electrode was amount of IL to the graphite. With further addition of IL, the void
kept at the potential of −1.2 V for 75 s during the accumulation spaces between the graphite particles are filled with excess IL. Sig-
step with solution being stirred using magnetic stirrer. Stripping nificant improvement in the surface structure of IL/CPE is observed.
step was performed with no stirring, by sweeping the potential in In Fig. 1c, the modified nanotube paste as the typical composite of
the positive direction up to +0.6 V. The measurements were per- the IL, MWCNTs and graphite can be observed. Fig. 1c contains a
formed for the series of Cd2+ , Pb2+ and Hg2+ ions solutions in the view of the particulate MWCNTs film spread all over the carbon
concentration range from 0.1 up to 150.0 nM. The peak currents surface. The dispersity of composite is suitable. The modification
were measured at −0.89 V for Cd2+ , −0.46 V for Pb2+ and +0.22 V of the CPE with IL and MWCNTs is clear. Fig. 1d displays a typical
for Hg2+ . All experiments were carried out at room temperature, morphology of PPh3 /MWCNTs/IL/CPE. As shown in this figure, PPh3
with purging with nitrogen for at least 5 min. did not change the morphology of MWCNTs/IL/CPE.

3. Results and discussions 3.2. Electrochemical impedance spectroscopy (EIS) study of

prepared electrodes
3.1. The surface morphologies of prepared CPEs
EIS is also a powerful technique to study the interface proper-
The surface morphology of the prepared electrodes plays a key ties of modified electrodes surface. If the Nyquist plot of impedance
role in the selective and sensitive detection of these analytes. The spectra includes a semicircle portion and a linear portion, the semi-
morphological features of the four electrodes were studies using circle portion at higher frequencies corresponded to the electron
SEM, as shown in Fig. 1. The unmodified CPE is characterized by a transfer limited process and the linear portion at lower frequen-
surface formed by irregularly shaped flakes of graphite that were cies corresponded to the diffusion process [25]. Fig. 2 exhibits the
isolated and a closer look of the film reveals a broken surface Nyquist plots of the CPE and modified CPEs.
(Fig. 1a). Fig. 1b shows a SEM image of IL/CPE with more uni- The equivalent circuit compatible with the Nyquist diagram
form surface topography and no separated carbon layers could be recorded for different electrodes in Fe(CN)6 3−/4− solution contain-
observed. The uniformity of the surface shows the good adherence ing 0.1 M KNO3 is depicted in Fig. 2 (inset). The equivalent circuit
of IL to graphite due to the high viscousness of IL. A layer of IL is can be described as solution resistance (Rs ) in series with the

Fig. 1. SEM images from surface of CPE (a), IL/CPE (b), MWCNTs/IL/CPE (c) and PPh3 /MWCNTs/IL/CPE (d).
 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460 455

Fig. 2. Nyquist plots for different electrodes in Fe(CN)6 3− /4− containing 0.1 M KNO3 : (a) unmodified CPE, (b) IL/CPE, (c) PPh3 /MWCNT/IL/CPE. Inset shows the equivalent
circuit compatible with the Nyquist diagram for this system.

parallel circuit of Faradic impedance (Zf ) and double layer capaci- but their peak currents were greater than that on the PPh3/CPE,
tance (Cdl ); Zf is composed of charge-transfer resistance (Rct ) and suggesting that the ionic liquid can effectually increase the rates
Warburg impedance (Zw ) which accounts for the Nernstian diffu- of metals preconcentration from aqueous solution to the surface
sion. In this study, the impedance spectra were recorded in the of the electrode. It is reported that the presented IL in the carbon
Nyquist plots (complex plane diagrams). Data fittings and simula- electrode not only acted as binder to fill in the blanks of the car-
tions were performed using a frequency response analyzer (Nova bon paste but also formed a layer of IL on the electrode surface
1.7, The Netherlands). Its value varies when the electrode surfaces [19]. Therefore, the IL in carbon electrode could facilitate the elec-
are modified by different substances. By fitting the electrochemi- tron transfer rate between the electrode surface and electroactive
cal impedance spectra to the equivalent circuit, the value of each species. Moreover, the signals at the PPh3 /MWCNTs/IL/CPE (blue)
electrical element in the equivalent circuit was obtained, as shown were remarkably enhanced than that at the other modified elec-
in Table S1 (Supplementary file). The results showed that there trode, which can be interpreted as that the adding of MWCNTs,
was almost no change in Rs and Zw , which demonstrated that they not only decreased the interfacial resistance, but also increased the
were not affected by the modification on the electrode surface. electrode contact area and enhanced the electrochemical proper-
The most obviously change was found in Rct . On the unmodified ties of the modified electrode. As can be seen, the peak currents
CPE, Rct was 670.1 . After a modification of electrode with IL, the of Cd2+ , Pb2+ and Hg2+ are more intense than that at the PPh3 /CPE.
value of Rct slight decreased to 421.6  that much lower than that This result indicated that more target metal ions were deposited on
on the unmodified CPE. The Rct of the CPE is larger than that of the electrode surface when the carbon nanotube paste electrode
the IL/CPE, because a layer of nonconductive paraffin oil as the was modified with the ionic liquid. This enhancement would be
binder was formed on the electrode surface inhibiting the elec- caused by both the large surface area and the special surface char-
tron transfer of the redox probe solution of [Fe(CN)6 ]3− /4− in 0.1 M acteristics, including the content of unsaturated suspending bonds,
KNO3 . The enhanced conductivity of the IL/CPE which employs the pentagons carbon loops, pentagon–heptagon defect pairs and other
conductive ionic liquid as the binder could be ascribed improved defects since these abundant active spots can caused interactions
performance. If further modified by MWCNTs and PPh3 , the value of between functional groups such as carboxylate and the analytes
Rct was 190.4 , remarkably decreased. This may mean that the IL at the electrode interface, as a result of specific adsorptions. This
and MWCNTs facilitated the electron transfer process on the elec- kind of interaction may pose effective chelation with enhanced
trode surface. The Rct value of final modified electrode was merely coordination which may provide lower detection limits. The com-
28.4% of the unmodified CPE. plexation behavior of metal ions at the interface and the possible
mechanism of preconcentration as well as stripping steps are given
3.3. Voltammetric behavior of metal ions as Scheme 1. Thus, high sensitivity, wide calibration range and well
separated stripping peaks were obtained. At the same time, ionic
Square-wave voltammograms of a solution containing Cd2+ ,
Pb2+ and Hg2+ in the KNO3 with pH 3.0 at the unmodified CPE
exhibited no any voltammetric peak either without prior pre-
concentration or following preconcentration onto the CPE by
accumulation potential −1.2 V for 75 s (Fig. 3). In the absence of
metal ions, the PPh3 -modified electrode did not show any stripping
peaks in the potential region −1.2 to +0.6 V. Therefore, the modified
electrode can be applied for the quantification of metal ions which
are active in this potential region. In presence of metal ions, the
PPh3 /CPE clearly showed well defined stripping (oxidation) peaks
for cadmium at −0.89, lead at −0.46 and mercury at +0.22 V and
with the peak to peak separations of 430 and 680 mV, respectively
(Fig. 3 purple). The interaction of modifier molecule with the metal
ions is an interfacial process which mainly depends on the nature of
the functionalities of the electrode surface. This separation between
SWV peaks is large enough and hence simultaneous determination
Fig. 3. Square wave anodic stripping voltammograms of cadmium, lead and mer-
of cadmium, lead and mercury ions were studied using the modified cury ions (40 nM) using various electrodes in 0.1 M KNO3 /0.1 M HCl solution of pH
electrode. On the PPh3/IL/CPE (Fig. 3 green), three peaks appeared 3.0. Accumulation time = 75 s. Preconcentration potential = −1.2 V.
456 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460

the redox reaction more reversible and increases the peak current.
Thus, Cd2+ , Pb2+ and Hg2+ can be induced to adsorb on the electrode
surface [27]. At upper concentrations of HCl, excess Cl– would form
coordination compounds with Hg2+ , resulting in the decrease of its
peak current. This case was reported in previous literature [28].
Also, the stripping peak of Hg2+ in 0.1 M KNO3 was ∼50 mV more
positive than in 0.1 M KNO3 /0.1 M HCl, but the sensitivity was sim-
ilar in both supporting electrolyte solutions. This behavior is in
agreement with the fact that the formation of chlorocomplexes of
Hg2+ favors the oxidation of Hg, which occurs at a less positive
potential [29]. According to these results, we chose 0.1 M KNO3 /0.1
HCl M as supporing electrolyte.
Moreover, the current peak intensities for Pb2+ and Cd2+ were
greater in the HCl supporting electrolyte than with the other acids,
even after changing their pH values from 3.0 to 5.0. Hydrochlo-
ric acid has been widely recommended for the determination of
several heavy metals by anodic stripping voltammetry [30].

3.3.2. Deposition potential

Deposition potential is an important parameter for stripping
techniques and has a significant effect on the sensitivity. The influ-
ence of deposition potential on the stripping response of Cd2+ ,
Pb2+ and Hg2+ ions were studied. The deposition potential was
Scheme 1. The suggested mechanism for the working principles of the fabricated
varied between −0.7 and −1.3 V under optimized pH condition.
PPh3 /MWCNTs/IL/CPE in 0.1 M KNO3 /0.1 M HCl solution containing Cd2+ , Pb2+ and The study showed that the stripping peak currents increase grad-
Hg2+ . (A) Metal ions in solution can be adsorbed or cooperated on the surface of ually when the deposition potential shifts from −0.70 to −1.2 V,
modified electrode; (B) reduction step; and (C) oxidation step (stripping). and three well-separated stripping peaks corresponding to Cd2+ ,
Pb2+ and Hg2+ are obtained with the relative higher peak currents
as −1.2 V is employed (Fig. S2). It has been noticed that the peak
liquid can promote the ions transfer rate. Therefore, more metal
current for each metal ion exhibits a remarkable dependence on
ions were deposited on the electrode surface in a shorter time.
the deposition potential. However, the deposition potential was
Because the response, ip , is influenced by many factors, it is nec-
selected for each cation in such way that intermetallic interferences
essary to optimize the parameters which may have any influence on
were minimized. On the other hand, when deposition potential
the measurement current so as to improve the quality of the analyt-
become more negative than −1.2 V, the peak currents decreases
ical results. The analytical parameters like supporting electrolyte,
due to the reduction of other chemicals at these potentials and
pH, deposition potential and deposition time which influence the
interfere in the determination of Cd2+ , Pb2+ and Hg2+ ions. Fur-
analytical response of the modified electrode were optimized in
thermore, as the deposition potential becoming more negative,
order to achieve the maximum efficiency of the developed sensor
the reproducibility of stripping currents for Cd2+ , Pb2+ and Hg2+
toward the metal ions quantification at trace level concentration.
became poor, because hydrogen evolution was beginning to be sig-
nificant in the medium at such negative potentials [7]. Also, the
3.3.1. Effect of supporting electrolyte and pH metals deposited on the electrode surface might be damaged by
Literature reports that the magnitude of the stripping current the hydrogen bubble and lead to decrease in current signals at very
for metal ions depends on the choice of the supporting electrolyte negative potentials. Hence in all further studies −1.2 V was used as
[26]. Generally, acidic medium was used as a supporting electrolyte an optimum deposition potential [7,30].
to determine the total heavy metals in real samples, to liberate any
complexes of metals and to avoid the adsorption of metal ions in
3.3.3. Accumulation time
the cell. The influence of different supporting electrolytes including
The effect of deposition time on the stripping responses of Cd2+ ,
KNO3 , HClO4 , HAc-NaAc, B-R universal buffer and PBS, were studied
Pb and Hg2+ ions was studied from 15 to 150 s and it has been
2+
using SWASV technique. As the result, the highest oxidation peak
found that the peak currents increase with increase of preconcen-
currents were observed when 0.1 M KNO3 was used as the sup-
tration time from 15 to 75 s. This is due to the fact that longer
porting electrolyte, and simultaneously the oxidation peak shapes
the preconcentration time caused more and more analytes get
were well defined and the background current was the lowest. The
accumulated at the electrode/solution interface onto functional-
effect of pH in this system was studied in the range 2.0–10.0; best
ized surface, hence current increases (Fig. S3). After 75 s, the peak
result was obtained at pH 3.0 using 0.1 M HCl solution for pH adjust-
currents becomes almost constant due to either surface saturation
ments (Fig. S1). The sensitivity and the separation of the peaks
or the attainment of equilibrium between the complexed metal
between Cd2+ , Pb2+ and Hg2+ ions were improved when this HCl
ions and the ions in solution [7,30]. Therefore, a preconcentration
was added. Changes in the HCl concentration over the range of
time of 75 s has been used in all further studies.
0.01–1.0 M affected the current intensity of either peak.
The stripping peak currents of Cd2+ , Pb2+ and Hg2+ were
obviously enhanced with the increase of HCl concentration from 3.3.4. Amount of PPh3
0.01 to 0.1 M. It may be due to in the presence of a low concentra- The effect of the amount of PPh3 within the MWCNTs/IL/CPE
tion of Cl− , one particular complex species present in the solution was evaluated. The use of PPh3 as modifier can greatly improve
adsorbed on the electrode surface to produce an adsorbed species the sensitivity and selectivity of determinations, which is due to
with the same chemical composition. It was also described that its functional sites. The peak current intensity was increased by
bounded chloride ions, present in the double layer around the elec- increasing the amount of PPh3 , because its concentration on the
trode, act as a bridge between the ions and the electrode. This makes surface of the modified electrode increased correspondingly. At 10%
 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460 457

(w/w) of modifier, the largest peak current was obtained. How-

ever, the continuous increase of the amount of modifier caused a
decrease in the peak current, because excessive amount of PPh3
may result in a decrease in the conductivity of the electrode. So the
best ratio of PPh3 in MWCNTs/IL/CPE composition was 10% (w/w).

3.3.5. Voltammetric parameters

In order to obtain well-defined SWASV response signals,
the voltammetric measurement parameters (pulse amplitude,
frequency and sweep rate) have also been optimized. These param-
eters are interrelated, having a combined influence on the peak
current response. The heights of Cd2+ , Pb2+ and Hg2+ increased
almost linearly with the increasing pulse amplitude but the res-
olution and the shape of the metals peaks also deteriorated above
50 mV. In the beginning the increase of the SW frequency resulted
in a relatively fast increase in the peak heights of Cd2+ , Pb2+ and
Hg2+ owing to the increase in the effective scan rate up to 20 Hz. (The
SW frequency together with the step potential defines an effective
scan rate.) However, above 20 Hz the peak currents started to level
off and the peaks to distort. The increase of the step potential did
not significantly enhance the peak heights of Cd2+ , Pb2+ and Hg2+
despite of the dramatic increase in the effective scan rate. At first
the peak currents raised with the step potential increasing then
reached a maximum and started to decrease. Therefore, the well-
shaped SWASV current peaks for quantitative measurements at low
metal ion concentrations were obtained at 50 mV pulse amplitude,
20 Hz frequency and 80 mV s−1 sweep rate.

3.4. Effect of interferences

The surface-active compounds present in the real samples might

interfere during the simultaneous voltammetric measurement of
the analytes. It was found that the surface-active compounds
adsorb at the electrode surface thereby decreasing the surface area
available for the interactions of metal ions with electrode surface.
To examine the interference due to surface-active compound, mea-
surements have been performed in the presence of humic acid,
CTAB, SDS and Triton X-114 (1 mg L−1 ). The presence of humic acid,
SDS and Triton X-114 do not interfere the simultaneous voltam-
metric measurement Cd2+ , Pb2+ , and Hg2+ . The cationic surfactant
CTAB exhibited the small decrease in the stripping currents owing
to electrostatic repulsion with metal ions. Such a minimization
of the surfactant’s fouling effect was in agreement with the good
antifouling ability of IL constructed carbon electrode. This charac-
teristic could be ascribed to the presence of a layer of IL film on the
graphite, which acts as a protective layer promoting the resistance
to fouling. Fig. 4. Square wave voltammograms using PPh3 /MWCNT/IL/CPE in 0.1 M
Intermetallic interference is very important in the determi- KNO3 /0.1 M HCl solution (pH 3.0) containing different concentrations of Cd2+ in the
presence constant concentration of Pb2+ and Hg2+ (40.0 nM) and under optimum
nation of some metal ions using anodic stripping voltammetric
conditions. (a). Inset shows calibration plot of the corrected electrochemical peak
methods. However, this type of interference can be overcome currents as a function of Cd2+ concentrations. Fig. 4b and c are related to Pb2+ and
by adjusting the deposition time to reduce the concentration of Hg2+ , respectively.
deposited species on the electrode surface or by setting the depo-
sition potential to a value where only the species of interest is
deposited and detected. The suggested method is advantageous 3.5. Simultaneous determination of Cd2+ , Pb2+ and Hg2+
since deposition time can be kept short so that the minimal
amounts of metals are incorporated onto the electrode surface. Square wave voltammograms are recorded to evaluate the elec-
The interference of some ions on the stripping voltammetric trochemical response of different concentration of Cd2+ , Pb2+ and
measurements was examined in 0.1 M KNO3 /0.1 M HCl containing Hg2+ when all the three species are present in the same solution.
10.0 nM Cd2+ , Pb2+ and Hg2+ . A 500-fold mass ratio of NO3 − , SCN− , For this purpose firstly the concentrations of lead and mercury
Cl− , F− , SO4 2− , Na+ , Ca2+ , Mg2+ , Al3+ , K+ , 400-fold mass ratio of Cu2+ , were kept constant at 40.0 nM while concentration of Cd2+ was
Mn2+ , Zn2+ , Cr3+ , Cr6+ , Fe3+ , Fe2+ , Ni2+ and Co2+ had no influence on varied from 0.1 to 150.0 nM. Fig. 4 shows the calibration curves
the signals of Cd2+ , Pb2+ and Hg2+ . It is noteworthy that the con- for analyte ions between 0.1 and 150.0 nM with error bars (N = 5).
centration levels of the interfering metals were very high when An examination of Fig. 4(a) shows that the anodic peak current for
compared with the concentration levels expected in unpolluted Cd2+ increased with an increase in Cd2+ concentration when the
waters. concentration of Pb2+ and Hg2+ was kept constant. Similarly, the
458 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460

Fig. 5. Square wave voltammograms of different concentrations of Cd2+ , Pb2+ and Hg2+ in 0.1 M KNO3 /0.1 M HCl solution (pH 3.0) using PPh3 /MWCNT/IL/CPE and under
optimum conditions. Inset shows calibration plot of the corrected electrochemical peak currents as a function of analytes concentrations.

influence of lead concentration was checked by increasing the Pb2+ of intermetallic complexes is unlikely. Such simultaneous detec-
concentration from 0.1 to 150.0 nM while fixing the cadmium and tion of Cd2+ , Pb2+ and Hg2+ without compromising the sensitivity
mercury concentration constant at 40.0 nM. As shown in Fig. 4(b), has not been reported in the literature. Thus, it can be concluded
keeping the concentration of Pb2+ constant, the anodic peak cur- that the proposed sensor can be successfully applied for the simul-
rent for lead was directly proportional to its concentration, while taneous determination of Cd2+ , Pb2+ and Hg2+ in real samples.
the peak currents related to the Cd2+ and Hg2+ did not change. Also,
the SW voltammogram for different concentrations of Hg2+ in the 3.6. Repeatability, reproducibility and stability of the modified
mixture of Cd2+ and Pb2+ was investigated when the concentration electrode
of Hg2+ changed, whereas the other was kept constant. The results
are shown in Fig. 4(c). Examination of the obtained results indicate The repeatability of the modified electrode was investigated by
that the peak current for each species systematically increases as repetitive recording its response at Cd2+ , Pb2+ and Hg2+ concen-
its concentration increased at a fixed concentration of other analyte trations of 1.0 and 15.0 nM. The relative standard deviation of the
ions (whose oxidation peak current remains fairly constant). peak currents for five replicate SWASV determinations of 1.0 and
The developed method was validated according to the ICH 15.0 nM of cadmium were 1.6% and 1.5%, respectively, and the cor-
guideline and found to be linear, sensitive, selective, precise and responding values for lead and mercury were 2.5, 2.3, 1.9 and 1.7%,
accurate [31,32]. The anodic peak current for Cd2+ was linearly respectively. The reproducibility of the electrode preparation pro-
dependent on its concentration (C) in the range from 0.1 to cedure was estimated by preparing five modified electrodes based
150.0 nM; a linear fitting regression equation was obtained [Ipa on the same fabrication procedure and applying for the simulta-
(␮A) = 0.15 + 0.585 C (nM)], with a 0.9989 correlation coefficient. neous determination of Cd2+ , Pb2+ and Hg2+ at 1.0 and 15.0 nM
The detection limit was 2.0 × 10−2 nM. The obtained detection concentrations. The corresponding RSD values were 2.9% and 2.4%
limits with a modified electrode were calculated based on three for Cd2+ , and 3.3, 4.2 and 3.1 and 2.8% for Pb2+ and Hg2+ , respec-
times the standard deviation of the blank (3sB ). The linear regres- tively. The results indicate that the modified electrode has high
sion equations for Pb2+ and Hg2+ covering the concentration reproducibility and excellent repeatability with this preparation
range in individual determination of each ion were obtained Ipa procedure and the voltammetric determinations. Also, with using
(␮A) = 0.05 + 0.289 C (nM) and Ipa (␮A) = 0.08 + 0.424 C (nM), with the PPh3 /MWCNTs/IL/CPE daily while storing the modified elec-
correlation coefficients 0.9954 and 0.9944, respectively. In this trode under ambient conditions, the electrode retained 95.6% of its
case, the detection limits for Pb2+ and Hg2+ were 4.1 × 10−2 and initial peak current response to 10 nM each of ion after a period of
2.8 × 10−2 nM, respectively. one month, indicating long-term stability of the electrode compos-
Square wave voltammograms with different concentrations of ite.
three metal ions in the same solution were also recorded and it was
found that when concentrations of the three analyte ions increase 3.7. Analysis of real sample
simultaneously, all three species exhibit oxidation peaks separately
without interfering each other. Also, the comparison of the cal- In order to illustrate application of suggested sensor in real sam-
ibration curves of Cd2+ , Pb2+ and Hg2+ , obtained individually or ples analysis, it was employed to detect Cd2+ , Pb2+ and Hg2+ in tap
simultaneously by SWV, also showed similar linear concentration and wastewater, soil, gasoline and dried fish samples. As can be seen
dependence and not only do not interfere with each other using from Tables 2 and 3, the results of the electrochemical experiments
suggested electrode but also the peak current values are exactly accorded very well with those obtained by ICP-OES, which con-
similar to those obtained from individual calibration plots with firmed the accuracy and reliability of the approach. The obtained
error bars of them (Fig. 5 and Table 1) indicating that the formation DLs are lower enough than given values of the Environmental
 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460 459

Table 2
Results for Cd2+ , Pb2+ and Hg2+ determination (nM) in water and gasoline samples obtained under the optimum conditions (N = 7).

Sample Analyte Added Found Recovery (%) ICP-OES

Tap water Cd(II) 0.00 1.31 (±0.09)a – ND* b

10.00 11.40 (±0.08) 101.0 ND
Pb(II) 0.00 35.72 (±0.10) – 34.50 (±0.18)
10.00 45.63 (±0.10) 99.0 45.86 (±0.15)
Hg(II) 0.00 0.21 (±0.08) – ND
10.00 10.32 (±0.12) 101.0 10.81 (±0.20)

Wastewater Cd(II) 0.00 72.14 (±0.04) – 71.60(±0.11)

10.00 81.96 (±0.05) 98.0 81.83 (±0.12)
Pb(II) 0.00 115.87 (±0.08) – 115.21 (±0.20)
10.00 126.02 (±0.07) 102.0 126.34 (±0.17)
Hg(II) 0.00 0.93 (±0.09) – ND
10.00 10.80 (±0.08) 99.0 10.76 (±0.16)

Gasoline Cd(II) 0.00 34.55 (±0.06) – 34.62 (±0.15)

20.00 54.12 (±0.04) 98.0 54.02 (±0.13)
Pb(II) 0.00 77.22 (±0.04) – 77.11 (±0.12)
20.00 97.63 (±0.03) 102.0 98.07 (±0.12)
Hg(II) 0.00 26.50 (±0.07) – 26.36 (±0.13)
20.00 46.87 (±0.07) 101.5 47.12 (±0.10)
a
Values in parentheses are S.D. based on seven replications.
b
Not detected.

Table 3
Results for Cd2+ , Pb2+ and Hg2+ determination (nM) in dried fish and soil samples obtained under the optimum conditions (N = 7).

Sample Analyte Added Found Recovery (%) ICP-OES

a
Dried fish 1 Cd(II) 0.00 6.71 (±0.15) – NDb
10.00 16.93 (±0.11) 102.0 ND
Pb(II) 0.00 7.64 (±0.17) – ND
10.00 17.53 (±0.12) 99.0 17.50 (±0.27)
Hg(II) 0.00 4.91 (±0.16) – ND
10.00 14.72 (±0.10) 98.0 14.81 (±0.24)

Dried fish 2 Cd(II) 0.00 0.42 (±0.10) – ND

10.00 10.61 (±0.13) 102.0 ND
Pb(II) 0.00 5.23 (±0.11) – ND
10.00 15.51 (±0.11) 102.9 15.32 (±0.15)
Hg(II) 0.00 2.11 (±0.12) – ND
10.00 12.20 (±0.10) 101.0 12.41 (±0.15)

Soil sample 1 Cd(II) 0.00 123.51 (±0.06) – 122.81 (±0.14)

20.00 143.13 (±0.05) 98.0 142.62 (±0.09)
Pb(II) 0.00 108.72 (±0.08) – 108.51 (±0.10)
20.00 128.91 (±0.05) 101.0 129.13 (±0.09)
Hg(II) 0.00 67.24 (±0.10) - 67.22 (±0.10)
20.00 87.82 (±0.06) 103.0 87.51 (±0.09)

Soil sample 2 Cd(II) 0.00 42.31 (±0.08) – 42.11 (±0.11)

20.00 62.82 (±0.06) 102.5 62.60 (±0.09)
Pb(II) 0.00 66.71 (±0.09) – 66.31 (±0.10)
20.00 86.32 (±0.06) 98.0 85.90 (±0.09)
Hg(II) 0.00 24.91 (±0.11) – 25.21 (±0.10)
20.00 45.52 (±0.09) 103.0 45.42 (±0.09)
a
Values in parentheses are S.D. based on seven replications.
b
Not detected.

Protection Agency (EPA) of the USA and of the European Union so the simultaneous voltammetric determination of neighboring
(EU) guidelines to determine trace metal concentrations [4]. It has elements is possible. Moreover, the multi ion determination in the
a great potential for the practical determination of Cd2+ , Pb2+ and presence of other ions in a very short deposition time required
Hg2+ in various real samples. no medium exchange or film deposition; this provides fast infor-
mation and can be easily adapted for on-field measurements. The
4. Conclusions found detection limits are lower than the permitted value of tar-
get ions reported by the EPA and EU in drinkable water. Moreover,
A simple, fast, reproducible and direct procedure was used for such a technique may certainly be a good alternative to ICP-OES,
the fabrication of a modified carbon paste electrode for the simul- CV-AAS and ETV-AAS, which, in the case of determination of the
taneous determination of Cd2+ , Pb2+ and Hg2+ in wide range of real analytes in complex matrices, needs too expensive and complex
samples. The obtained results suggest that PPh3 /MWCNTs/IL is a system equipment. Also, no paper has reported simultaneous elec-
promising material which possesses the advantages in compari- trochemical determinations of Cd2+ , Pb2+ and Hg2+ in real samples
son with other suggested electrodes in electrochemically detecting such as tap water, waste water, gasoline, fish and soil samples.
heavy metal ions with detection limits in the range of sub nano The obtained results agree well with those of ICP-OES. These made
molar, high selectivity and a long-term usage possibility. The peak the system promising to be used in routine analytical applica-
potentials of each metal are well defined and sufficiently separated tions.
460 H. Bagheri et al. / Sensors and Actuators B 186 (2013) 451–460

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metal sensing and detection, Analyst 136 (2011) 4383–4391. research interests are based within the fields of analytical, bioanalytical and envi-
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electrode for anodic stripping voltammetric determination of lead: An elec- ical species.
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