Journal of Hazardous Materials 190 (2011) 451–459

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Preparation of nano-sized Pb2+ imprinted polymer and its application as the

chemical interface of an electrochemical sensor for toxic lead determination in
different real samples
Taher Alizadeh ∗ , Somaye Amjadi
Department of Applied Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil, Iran

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

Article history: In this work, a new nano-structured ion imprinted polymer (IIP) was synthesized by copolymerization of
Received 5 November 2010 methacrylic acid–Pb2+ complex and ethylene glycol dimethacrylate according to the precipitation poly-
Received in revised form 7 March 2011 merization. Methacrylic acid acted as both functional monomer and complexing agent to create selective
Accepted 18 March 2011
coordination sites in a cross-linked polymer. A carbon paste electrode modified with IIP-nanoparticles
Available online 27 March 2011
was used for fabrication of a Pb2+ sensitive electrode. Differential pulse stripping voltammetry method
was applied as the determination technique, after open circuit sorption of Pb2+ on the electrode and its
Keywords:
reduction to metallic form. The IIP modified electrode showed a considerably higher response, compared
Pb2+
Imprinted polymer
to the electrode embedded with non-imprinted polymer (NIP). This indicated that the suitable recogni-
Differential pulse voltammetry tion sites were created in the IIP structure in the polymerization stage. Various factors, effective on the
Electrochemical sensor response behavior of the electrode, were investigated and optimized. The introduced sensor showed a
linear range of 1.0 × 10−9 to 8.1 × 10−7 M and detection limit of 6.0 × 10−10 M (S/N = 3). The sensor was
successfully applied for the trace lead determination in different samples.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction trothermal atomic absorption spectrometry, inductively coupled

plasma-mass spectrometry (ICP-MS), hydride generation atomic
Lead is an important environmental pollutant, found in soil, absorption spectrometry and flame atomic absorption spectrom-
water and air with no biological function, but many toxicological etry (FAAS) [7–15].
effects to human life [1–3]. The determination of lead is difficult On the other hand, different kinds of sensors including optical
due to its low concentrations in environmental samples [2]. Lead, [16], potentiometric [17,18] and voltammetric [19,20] sensors have
is distributed widely in nature and enters our body system through been widely used for lead determination. However, voltammetric
air, water, and food. The toxicity of lead has been studied exten- methods are highly favorable techniques for the determination of
sively. Pb2+ binds with the –SH group in enzymes or proteins and metal ions because of its low cost, high sensitivity, easy operation
acts as an enzyme inhibitor. It interferes with calcium metabolism and the ability for portability. Stripping analysis of lead have been
and gets deposited in bone. Lead poisoning in humans causes severe reported by using different electrodes such as silver electrode [19],
damage in kidneys, liver, brain, reproductive system, central ner- bismuth/poly (-amino benzene sulfonic acid) film electrode [20],
vous system and sometimes causes death. All these findings cause boron-doped diamond electrode [21], mercury film supported on
great concern regarding public health, demanding accurate deter- wax impregnated carbon paste electrode [22], Gold electrode [23]
mination of this metal ion at trace and sub-trace levels [4–6]. and titanium dioxide [24].
Great efforts have been made to analyze lead in trace levels In order to enhance the sensitivity and selectivity of the electro-
by means of a wide range of spectrometric methods such as elec- chemical determination of lead(II), chemically modified electrodes
trothermal atomization atomic absorption spectrometry (ET-AAS), have received increasing attentions in the past decades. The mod-
sequential multi-element flame atomic absorption spectrometry, ifiers used include bismuth [25–42], organic chelating groups
graphite furnace atomic absorption spectrometry (GFAAS), elec- [43–50], clay nano particles [51], SiO2 –Al2 O3 mixed-oxide [52],
zeolite [53], PAN-incorporated nafion [54] and silica [55].
However, most of these procedures have difficulties achiev-
ing the sensitivity required for the determination of low levels of
∗ Corresponding author at: Department of Applied Chemistry, Faculty of Science,
lead(II) ion in some real samples. Moreover, these materials do not
University of Mohaghegh Ardabili, Daneshgah street, 56199-11367, P.B. 179, Ardabil,
Iran. Tel.: +98 0451 5514702; fax: +98 0451 5514701. provide a suitable selectivity toward Pb2+ in the presence of some
E-mail addresses: Alizadeh@uma.ac.ir, taa 55@yahoo.com (T. Alizadeh). potential interfering species like Cu2+ , Ag+ , etc. Therefore, there is

0304-3894/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2011.03.067
452 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459

still an urgent demand to introduce a high selective modifier for particles, obtained after polymerization, were firstly washed with
using in this field. ethanol and then with HCl solution (2 M). Thiourea solution (0.1 M)
Molecular imprinting is a promising technique for the prepara- was also used for removal of target ions from the polymer parti-
tion of polymers with predetermined selectivity and high affinity cles. Finally, the particles were washed several times with distilled
[56,57]. Molecularly imprinted polymers (MIP) demonstrate very water and dried at 60 ◦ C. The non-imprinted polymer (NIP) was
good thermal and chemical stability and can be used in aggres- prepared using the same protocol except that Pb(II) did not exist in
sive media [58]. These materials possess several advantages over the polymerization mixture.
their biological counterparts including low cost, ease of prepara-
tion, storage stability, repeated operations without loss of activity, 2.3. Preparation of the sensors
high mechanical strength, durability to heat and pressure, and
applicability in harsh chemical media. MIP has become increasingly In order to prepare the sensor (IIP-CP), 0.03 g graphite was
attractive in many fields of chemistry and biology, particularly as an homogenized in a mortar with 0.007 g of powdered IIP for 10 min.
affinity material for sensors [59–63], binding assays [64], artificial Subsequently, n-eicosane (0.015 g) was melted in a dish, heated at
antibodies [65,66], adsorbents for solid phase extraction [67–71], 45–50 ◦ C. The graphite/IIP blend was then added to the melted n-
and chromatographic stationary phases [72–75]. eicosane and mixed with a stainless steel spatula. The final paste
On the other hand, ion-imprinted polymers (IIPs) are similar to was used to fill a hole (2.00 mm in diameter, 3 mm in depth) at
MIPs but, they recognize metal ions after imprinting, while retain- the end of an electrode body, previously heated at 45 ◦ C. After
ing all the virtues of MIPs. The production of polymers exhibiting cooling at room temperature, the excess of solidified material
selective binding of a specific cation, involves the formation of cav- was removed with the aid of a paper sheet. The electrode can be
ities equipped with complexing agents so arranged as to match the reused after each experiment by moving of the electrode surface
charge, coordination number, coordination geometry and size of on a paper sheet in order to extrude a thin layer of the electrode
the target cation [76]. surface.
Different kinds of imprinted polymers have been reported for
recognition of lead ions [77–79]. 2.4. Determination procedure
We have recently reported several papers describing the
application of MIP particles as a recognition element of the electro- The prepared electrode was inserted into the solutions contain-
chemical sensors such as voltammetric and potentiometric sensors ing the Pb2+ (pH 5.8), being at stirring state (500 rpm). Then, the
for different kinds of molecular analytes [80–83]. In this study, electrode was inserted into the washing solution (water, neutral),
a lead imprinted polymer, as an ion recognition material, was remaining in this solution for 15 s. The electrode was finally placed
synthesized by a new formulation. According to the IIP synthe- in the electrochemical cell containing 10 mL of HCl (0.12 M). At firs,
sis method, Pb2+ was first extracted into acetonitrile as Pb (MAA)2 a negative pre-potential of −1.4 V was applied to the electrode for
and then the polymerization was started in the presence of ethy- 15 s to reduce the recognized target ions and then the differential
lene glycol dimethacrylate as cross-linking agent. By this means, pulse stripping voltammetry was performed in the potential range
the Pb2+ selective cavities with carboxylic acid coordination sites of −0.8 to −0.3 V.
were created in the cross-linked polymer. The prepared Pb2+ -IIP
was subsequently applied for preparation of IIP based sensor. 3. Results and discussion

3.1. Pb(II) ion imprinted polymer

2. Experimental
In order to prepare IIP, 4 mmol of Pb(CO3 )2 was contacted
2.1. Instrument and reagents
with methacrylic acid, dissolved in acetonitrile. Lead carbonate
was not soluble in acetonitrile. However, interaction of Pb2+ with
Electrochemical data was obtained with a three-electrode sys-
methacrylic acid resulted in lead-methacrylate complex that could
tem using a potentiostat/galvanostat model PGSTAT302, Metrohm.
be transferred into acetonitrile. Precise determination (titration
The carbon paste electrodes modified with IIP or non-imprinted
with EDTA) showed that 1.6 mmol of primarily used Pb2+ (4 mmol)
polymer (NIP) was used as a working electrode. A platinum wire
could be transferred to acetonitrile in the form of Pb(methacrylate)2
and an Ag/AgCl electrode were used as the counter and reference
during the described experiment. After addition of EGDMA and ini-
electrodes, respectively.
tiator, the polymerization reaction was started. Scanning electron
Methacrylic acid (Merck, Germany) and ethylene glycol
microscopy image of the obtained polymer particles is shown in
dimethacrylate (EDMA) (Sigma–Aldrich, USA) were purified by dis-
Fig. 1. As can be seen, the sizes of synthesized polymer particles are
tillation under reduced pressure. 2,2 -(2-methyl propionitrile) was
at nano-scale range. Different polymeric particle sizes ranged from
obtained from (Acros Organic, Geel, Belgium) and used as an initia-
about 50 nM to approximately 500 nm can be distinguished in the
tor. Pb(NO3 )2 were from (Merck, Germany). Other chemicals were
depicted image.
of analytical grade and were purchased from (Merck, Germany).
There was no considerable difference among the FT-IR spectra
of the examined polymers in all recorded regions except the region
2.2. Pb(II) imprinted polymer preparation of ∼1500–1700 cm−1 . FT-IR spectra of the unleached IIP, leached IIP
and also NIP are shown in Fig. 2(a), (b) and (c), respectively. Pres-
In order to prepare Pb(II) imprinted polymer, 4 mmol of ence of strong stretching vibration band at ∼1721 cm−1 is related
Pb(CO3 )2 (prepared by reaction of Pb(NO3 )2 and Na2 CO3 ) and to the C O of carboxylic acid group of methacrylic acid, situated
12 mmol of methacrylic acid were contacted with 20 mL acetoni- mainly at the surface of polymeric particles. This band can be seen
trile and then the mixture was stirred for 24 h. The mixture was then in all examined polymers. Though, there is no band in the region
centrifuged and the supernatant was separated for polymer prepa- of 1500–1700 cm−1 for NIP, an evident band for the unleached IIP
ration. Then, 22 mmol EGDMA and 0.02 g initiator were dissolved can be observed at the mentioned region (∼1610 cm−1 ), ascribed
in 5 mL acetonitrile and then added to the previous solution. The to the –C O, linked to Pb2+ via coordination bonding. This band is
resulting mixture was purged with N2 gas for 10 min. The polymer- less strong than that is located at ∼1721 cm−1 because, these types
ization was carried out in water bath at 70 ◦ C for 24 h. The polymeric of –C O groups are mainly situated in the interior sections of IIP
 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459 453

3.2. Comparison of the IIP-CP electrode with NIP-CP electrode and

evaluation of the washing effect on the responses of the electrodes

The carbon paste electrode modified with IIP or NIP was incu-
bated in the Pb2+ solution meanwhile the solution was stirred
continuously. Then, the electrode was inserted into the elec-
trochemical cell and a negative potential was applied to the
electrode. Subsequently, differential pulse voltammetry technique
was applied for the determination of lead. In order to evaluate the
washing effect on the electrode responses, the IIP-CP and NIP-CP
electrodes were inserted in different washing solution for 10 s, after
being removed from the Pb2+ solution. The obtained voltammetric
signals of the two mentioned electrodes were shown in Fig. 3. It
can be seen that the obtained signal for IIP-CP (voltamogram, a)
electrode is higher noticeably than that of NIP-CP electrode (volta-
mogram, d), indicating the existence and properly functioning of
Fig. 1. Scanning electron microscopy images of prepared of IIP. the selective cavities in the IIP, created in the polymerization step.
Washing of the electrodes, after removing them from the analyte
solution, decreases both electrode signals, indicating removal of
particles. It can be seen that the washing of the IIP and removal of weakly adsorbed ions from the IIP and NIP surface sites. It is also
Pb2+ leads to a considerable decrease at the height of vibration band clear that the thiourea washing solution decreases both IIP-CP and
of the –C O coordinated to Pb2+ . These observations can be a right NIP-CP signals more than pure water. Also, in this case, the response
evidence for the presence and properly interaction of the selec- difference between IIP-CP and NIP-CP electrodes is decreased con-
tive recognition sites in the IIP particles which are created during siderably. This implies that the thiourea solution interfere with
imprinting process. selective sites of IIP for conserving adsorbed Pb2+ ions. Therefore,

Fig. 2. FT-IR spectra recorded for unleached IIP, leached IIP and NIP.
454 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459

we decided to use pure water in place of thiourea for electrode

washing.

3.3. Evaluation of the selectivity of IIP-CP electrode

The selectivity of Pb2+ imprinted polymer in the IIP-CP compo-

sition was investigated by incubation of the electrode in different
solutions containing a mixture of Pb2+ (5 × 10−7 M) and some other
cations at various concentrations and subsequently electrochem-
ical analyzing. The obtained results are shown in Fig. 4(a), (b), (c)
and (d). It can be seen that the presence of Cu2+ , Cd2+ and Fe2+ in the
Pb2+ solution, at the identical concentrations, does not significantly
influence the voltammetric response of Pb2+ . It is clear that Cd2+
cannot interfere with the Pb2+ signal even at 25-fold molar excess
although, at this concentration ratio a detectable signal for Cd2+ is
observed. This indicates that the essential selective sites in the IIP
are affected by the Cd2+ and thus these foreign ions are extracted at
the sites with lower selectivity. However, at 50-fold molar excess,
Cd2+ affects significantly the signal of Pb2+ , indicating the presence
of competition between these ions for capturing the high selective
cavities in the IIP. The same behaviors can be seen in the case of Fe3+
and Cu2+ . However, the interference threshold is different from that
Fig. 3. Comparison of differential pulse voltammetry responses of IIP-CP elec- of Cd2+ . In these cases the interference indication appears at about
trode and NIP-CP electrodes with and without washing steps; [Pb2+ ] = 5 × 10−7 , 15-fold molar excess. It can be seen that the addition of CN− can
extraction time = 15 min, stirring rate = 700 rpm; stripping voltammetry conditions: nullify the interference effect of Cu2+ in the determination of Pb2+
E-conditioning = −1.0 V, conditioning time = 20 s, E-step = 0.01 V, E-pulse = 0.1 V,
by the developed sensor. Here, although the Cu2+ interfere with
pulse time = 0.01 s, Scan rate = 0.1 V s−1 .
the Pb2+ at 15-fold molar excess, however the presence of CN− in
the solutions decrease intensively the effect of even 100-fold molar
excess of Cu2+ in the Pb2+ solution. In the case of Hg2+ (Fig. 2(d)),

Fig. 4. Comparison of the electrode selectivity for Pb2+ ion in the presence of different interfere ions at various concentrations; [Pb2+ ] = 5 × 10−7 , extraction time = 15 min, stir-
ring rate = 700 rpm; stripping voltammetry conditions: E-conditioning = −1.0 V, conditioning time = 20 s, E-step = 0.01 V, E-pulse = 0.1 V, pulse time = 0.01 s, Scan rate = 0.1 V s−1 .
 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459 455

Fig. 5. the effect of electrode composition on its response, extraction time = 15 min, stirring rate = 700 rpm; stripping voltammetry conditions: E-conditioning = −1.0 V,
conditioning time = 30 s, E-step = 0.01 V, E-pulse = 0.1 V, pulse time = 0.01 s, Scan rate = 0.1 V s−1 .

it can be seen that the presence of 100-fold excess of this ion can- and NIP-CP electrodes although, the variation in the NIP-CP signal
not affect significantly the Pb2+ signal. These observations indicate with changing of carbon content of the electrode is not so con-
that a sophisticated arrangement of carboxylic acid groups in the siderable. Higher amounts of carbon can decrease the number of
pre-designed cavity of an IIP leads to an interesting selectivity for selective sites of IIP in the electrode surface, resulting in interfer-
the target ion. ence in target ions extraction in the electrode surface. On the other
hand, lower amount of carbon leads to a decrease in conductivity of
3.4. The effect of IIP-CP composition on its response the electrode and thus decreasing the rate of electron transferring.
It can be seen that the presence of higher amounts of binder (n-
In order to find the best composition for IIP-CP electrode, the eicosane) in the IIP-CP electrode leads to a decrease in the electrode
amount of different components of the electrode including IIP, response. When the binder amount reaches to 0.0205 g, it can be
carbon and n-eicosane was changed in the fixed conditions of seen that the IIP-CP signal is as much as that of NIP-CP signal. This
extraction and voltammetric determination and then the obtained is due to the decreasing of the electrode surface conductivity by
responses were used for conclusion. In order to obtain suitable increasing the binder amount that acts as an insulating material in
results for final conclusion, the response of NIP-CP electrode, pre- the electrode surface.
pared at the conditions similar to IIP-CP electrode, was compared
with that of IIP-CP electrode. 3.5. Evaluation of the effect of Pb2+ extraction conditions on the
As shown in Fig. 5(I), the IIP-CP signal is enhanced as the IIP electrode response
content of the electrode is increased. On the other hand, increasing
of NIP amount in the NIP-CP electrode does not influence the elec- In order to optimize the stirring rate in the extraction period,
trode signal and the electrode retains its initial signal. Therefore, Pb2+ was extracted in the prepared IIP-CP electrodes at various stir-
the increasing of IIP amount in the electrode increases the selective ring rates, whereas the other extraction parameters were the same
recognition cavities in the electrode, increasing the capacity of the and constant. The obtained results showed that the greater the
electrode surface for target ion up-taking. In spite of the depicted stirring rate, the higher the electrode response for Pb2+ , indicating
results in Fig. 5(I), it was found that the physical property of the considerable effect of the stirring rate on the Pb2+ extraction in the
surface of the final electrode was not practically suitable by using IIP-CP electrode. The growth in target ion voltammetric response
of IIP higher than a determined amount. Thus, 0.017 g was selected with the stirring rate increasing continued up to 500 rpm. However,
as optimal for IIP amount in the IIP-CP electrode. The effect of car- further enhancement in stirring rate did not affect considerably
bon and n-eicosane amounts on the prepared electrode response the extraction amount. Therefore, the stirring rate of 500 rpm was
was investigated by varying of these parameters amounts in the chosen as optima for this variation.
IIP-CP and NIP-CP electrodes, followed by recording the obtained The increasing of the sample volume led to higher electrode
signals. The results are shown in the Fig. 5(II) and (III). It can be response. However, after an optimum amount, increasing of sam-
seen that, there is an optimum amount for carbon in both IIP-CP ple volume decreased the electrode response because of lowering
456 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459

Table 1
Interference levels for some tested ions in the determination of Pb(II) by developed
sensor.

Species Interference level

Alkali and earth-alkali No interference

Co2+ , Zn2+ , Ni2+ , Cr3+ , Hg2+ , Ag+ No interference
Cd2+ >50
V3+ , Mn2+ >100
Cu2+ , Fe2+ >10

No interference: no interference effect even at 200-fold molar excess of the aimed

foreign ion.

However, at more negative potentials the reduction of solvent can

interfere with the target ions reduction and this can lead to reduced
signal of the electrode.

3.7. Analytical characterization

Fig. 6. the effect of Pb2+ solution pH on the IIP-CP electrode response. After the optimization and establishment of the determination
method for the prepared IIP-CP sensor, various species were exam-
ined with respect to their interference with the determination
the target ion extraction in the electrode. Thus, 30 mL was selected of Pb2+ . In this sensor, the preconcentration of Pb2+ involves the
as an optimal for sample volume. adsorption of Pb2+ at open circuit potential, followed by the strip-
The effect of pH of extraction solution on the Pb2+ extraction in ping/detection step which is performed in a clean medium. This is
the electrode was also studied. For this purpose, the prepared elec- advantageous in eliminating the interferences during the stripping
trode was inserted into the solutions with various pH values where step because, many interference species can be left in the sample
they were incubated for 10 min at the constant stirring rate. After solutions. However, during the preconcentration step, interference
the mentioned time, the electrode was removed from the solution may be caused by competitive adsorption of the metal ions to the
and immersed into the solution of the electrochemical cell. The binding sites of IIP.
result of this experiment is shown in Fig. 6. As can be seen, the pH The tolerance limit was established as the maximum concen-
condition fixing seems to be an urgent task in this work. As can tration of foreign species that caused a relative error of 5% in
be seen the best pH for Pb2+ extraction in the electrode is equal to the analytical signal. For 50 nM of lead(II), the detected interfer-
5.8. At higher and also lower pH, the electrode response decreases ence levels for different agents are shown in Table 1. As can bee
sharply. The response lowering at acidic pH can be attributed to seen, the presence of alkaline and earth alkaline cations as well as
the protonation of carboxylic groups of complexing agent present some potential interfering cations such as Co2+ , Zn2+ , Ni2+ , Cr3+ ,
in the selective cavities of IIP, decreasing the complexing capabil- Hg2+ do not significantly influence the electrode signal. 50–fold
ity of Pb(II) with the IIP sites. Diffusion of the counter ions into the excess of Cd2+ and 10-fold excess of Fe3+ and Cu2+ influence sig-
pores of IIP, at alkaline pH, can probably swell the IIP and reduce nificantly the prepared sensor response. It was found that adding
the interaction of Pb(II) with selective cavities, reducing the elec- of CN− (0.005 M) in the Pb2+ solution can decrease the interfer-
trode signal in alkaline pH media. Therefore, precisely adjustment ence effect of Cu2+ and Fe3+ without influencing the Pb2+ signal. By
of pH is of most important. The phosphate buffer was applied for this means, the interference levels were reached to 100-fold and
adjusting the pH of extraction. 25-fold excess for Cu2+ and Fe3+ , respectively. In order to evaluate
The increasing of extraction time led to an intensive increase in the reproducibility of the IIP-CP electrode, 50 nM of Pb2+ solution
the Pb2+ extraction amount in the electrode till about 30 min. After, was determined by five separately produced electrodes. This way,
the response increasing rate with time enhancement was not so a RSD% equal to 2.6 was calculated for the described determination.
considerable. In order to decrease the Cd2+ analyzing time, as much Moreover, five separate determinations of Pb2+ by the same elec-
as possible, the time of 30 min was selected for the extraction time. trode resulted in a RSD% = 3.4 (n = 5). This can be an indicative of the
repeatability of the method. In this case, the next determination by
3.6. Optimization of the pre-potential magnitude and its applied the electrode was carried out after renewing the electrode surface
time by polishing the electrode surface on a paper sheet. The calibra-
tion graph (shown in Fig. 7) of the prepared sensor showed a linear
In this work, a definite pre-potential was applied to the elec- relationship over Pb2+ concentration in the range of 1.0 × 10−9 to
trode for a determined time and then the potential was scanned for 8.1 × 10−7 M with a detection limit of 6.0 × 10−10 M (S/N = 3). Each
recording the oxidation peak. It is clear that the pre-potential mag- point of the calibration graph is the average of three replications.
nitude and its applying time can influence the sensor performance. The detection limits of 5.0 × 10−8 M and 1.0 × 10−7 M were also
Thus, the effect of these parameters on the response magnitude of calculated for the NIP-CP and CP electrodes, respectively.
the developed sensor was investigated. Increasing of the time of the
applied pre-potential (−1.0 V) in the time range of 20–60 s resulted 3.8. Determination of Pb2+ in real samples by proposed sensor
in slightly increase in the electrode response. However, higher than
60 s the electrode response started to considerably decrease, prob- Determination of lead(II) was carried out in real water sam-
ably due to the diffusion of species far from the electrode surface. ples. The samples were tested before addition of lead(II) with the
Therefore, a pre-potential time of 50 s was chosen for the sensor. optimized sensor and it was found that the tap and river water sam-
On the other hand, the variation of the electrode response with ples were lead(II) free. Thus, 50 mL of those samples was spiked
pre-potential magnitude changing showed an optimum at −1.4 V. with different concentrations of lead(II). Then, the determination
Increasing the negative potential magnitude, applied to the elec- method was executed step by step, according to the proposed pro-
trode, increases the rate of reduction in the electrode surface. cedure. The edible refined salt samples were prepared by dissolving
 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459 457

Table 2
Determination of Pb(II) in different samples by the IIP-CP electrode and ICP technique.

Sample IIP-CP sensor (n = 4) ICP (n = 3)

Spiked (nM) Found (nM) Recovery (%) Found (nM)

Tap water 100.0 114.0(±3.1) 114.0 108.0(±5.80)

54.1 59.1(±2.1) 110.0 –
16.7 15.5(±0.7) 93.0

River water 100.0 107.0(±3.7) 107.0 –

54.7 51.7(±1.9) 95.0 55.1(±3.58)
16.7 15.7(±0.8) 94.0 –

Salt – 0.65a (±0.03) –

1a 1.57a (±0.05) 95.0

Wastewater – 2.54b (±0.08) 2.71b (±0.18)

1b 3.66b (±0.13) 3.37b (±0.22)
a
␮g g−1 .
b
␮M.

Table 3
Comparison of the IIP-CP electrode with some previously reported Pb2+ voltammetric sensors.

Electrode Linear range Detection Interference level [Ref]

limit
2+ 2+ 2+ 3+
Hg Cu Cd Fe

Carbon paste modified with 2–10,000 1 >100 <1 >30 >100 [47]
1,4-bis(prop-2 -enyloxy)-9,10-Anthraquinone
Screen-printed electrodes modified with functionalized 0–480 4.3 – <1 – – [84]
mesoporous silica
Carbon electrode modified with montmorillonite-bismuth 4.8–115 0.96 <1 <1 – – [85]
Boron-doped diamond electrode 2–100 2 – <1 – – [21]
Bismuth/poly (p-aminobenzene sulfonic acid) film electrode 4.8–627 3.8 >50 >30 – >30 [20]
Gold-based screen-printed sensor 0–240 2.4 <1 <1 <1 – [23]
Bismuth nanoparticle modified boron doped diamond electrode 96–960 9.2 – – – – [39]
Carbon paste modified with organofunctionalised SBA-15 300–7000 40 – – >2.5 – [55]
nanostructured silica
Cyclodextrin-modified gold electrodes 17–930 7.1 – – <1 – [48]
Screen-printed carbon electrode modified with 0–3378 72 – <1 – – [43]
1-(2-pyridylazo)-2-naphthol modified
Carbon paste modified with zeolite 25–100 17.3 <1 <1 <1 <1 [53]
IIP-CP electrode 1–810 0.6 No >10 >50 >10 This work

a determined amount of the salt in water. It was found that this sam- developed method and then spiked with a known amount of Pb2+
ple contained trace level of Pb2+ . Thus, the salt pb2+ content was solution, followed by re-determination of Pb2+ . In order to verify
first determined according to the obtained signal and then it was the validity and applicability of the method the Pb2+ content of
spiked with a determined amount of Pb2+ , followed by calculation some of the previously analyzed solutions, were determined by
the percent recovery. Moreover, a wastewater sample suspected inductively coupled plasma-atomic emission spectroscopy (ICP-
to contain a considerable amount of Pb2+ was analyzed by the AES) technique and the results were compared with those of our
developed technique. The results of aforementioned studies are
summarized in Table 2 and clearly certify the applicability of this
method for determination of Pb2+ in various real samples.

3.9. Comparison of IIP-CP electrode with some of the previously

reported Pb2+ voltammetric sensors

A number of analytical characteristics of the IIP-CP sensor were

compared with those of some previously reported voltammetric
Pb2+ sensors. The results are summarized in Table 3. As can be
seen, the IIP-CP electrode shows very good analytical character-
istics, compared to majority of the depicted sensors. Although, the
IIP-CP electrode offers the lowest detection limit among the con-
sidered electrodes; perhaps, the main advantage of this electrode
is its highly resistance capability against the interference effect of
some potential interfering ions such as Cu2+ which in most cases
interfere whit Pb2+ determination even at concentration lower than
that of Pb2+ .

4. Conclusion

Fig. 7. calibration curve of the developed mercury ion sensor in the optimized In this paper a new electrochemical sensor for determination of
conditions; inset: the linear range of the calibration curve. lead ions at trace levels was introduced. Application of IIP as a novel
458 T. Alizadeh, S. Amjadi / Journal of Hazardous Materials 190 (2011) 451–459

modifying agent in the carbon paste electrode made it very selec- on wax impregnated carbon paste electrode Assessment of quantification
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