Talanta 142 (2015) 221–227

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Sensitive voltammetric determination of lead released from ceramic

dishes by using of bismuth nanostructures anchored on biochar
Deonir Agustini a, Antonio Salvio Mangrich b,c, Márcio F. Bergamini a,
Luiz Humberto Marcolino-Junior a,n
a
Laboratório de Sensores Eletroquímicos (LabSensE), Departamento de Química, Universidade Federal do Paraná (UFPR), CEP 81.531-980 Curitiba-PR, Brazil
b
Laboratório de Química de Húmus e Fertilizantes, Departamento de Química, Universidade Federal do Paraná (UFPR), CEP 81.531-980 Curitiba-PR, Brazil
c
Instituto Nacional de Ciência e Tecnologia de Energia e Ambiente (INCT/CNPq), Brazil

art ic l e i nf o a b s t r a c t

Article history: A simple and sensitive electroanalytical method was developed for determination of nanomolar levels of
Received 15 March 2015 Pb(II) based on the voltammetric stripping response at a carbon paste electrode modified with biochar (a
Received in revised form special charcoal) and bismuth nanostructures (nBi-BchCPE). The proposed methodology was based on
16 April 2015
spontaneous interactions between the highly functionalized biochar surface and Pb(II) ions followed by
Accepted 17 April 2015
Available online 27 April 2015
reduction of these ions into bismuth nanodots which promote an improvement on the stripping anodic
current. The experimental procedure could be summarized in three steps: including an open circuit pre-
Keywords: concentration, reduction of accumulated lead ions at the electrode surface and stripping step under
Bismuth nanostructures differential pulse voltammetric conditions (DPAdSV). SEM images revealed dimensions of bismuth
Electrochemical sensor
nanodots ranging from 20 nm to 70 nm. The effects of main parameters related to biochar, bismuth and
Lead
operational parameters were examined in detail. Under the optimal conditions, the proposed sensor has
Ceramic dishes
exhibited linear range from 5.0 to 1000 nmol L
1 and detection limit of 1.41 nmol L
1 for Pb(II). The
optimized method was successfully applied for determination of Pb(II) released from overglaze-deco-
rated ceramic dishes. Results obtained were compared with those given by inductively coupled plasma
optical emission spectroscopy (ICP-OES) and they are in agreement at 99% of confidence level.
& 2015 Published by Elsevier B.V.

1. Introduction
Lead is one of the most useful metals used since ancient civi-
lizations because of its abundance, low cost and ease in their
applications [1]. However, it is characterized by serious effects on
human health being absorbed and accumulated in the body,
affecting heart, bones, intestines, kidneys, reproductive and ner-
vous systems [2], lag in learning and low neurological develop-
ment in children [3]. Although several efforts have been made to
reduce the exposure to this metal, a large number of people con-
tinue being polluted by lead due to many sources of exposure like
paints, water, food, dust, soil, kitchen utensils and leaded gasoline
[4]. For these reasons, the determination of traces of lead in different
matrices has a great importance. The certified standard techniques
include electrothermal atomic absorption spectrometry (ET-AAS),
flame atomic absorption spectrometry (FAAS), inductively coupled
plasma mass spectrometry (ICP-MS) and inductively coupled plasma
optical emission spectrometry (ICP-OES) [5–7]. Although these
n
Corresponding author. Tel.: þ 55 41 3361 3177; fax: þ55 41 3361 3186.
E-mail address: luiz1berto@ufpr.br (L.H. Marcolino-Junior).
techniques are very sensitive, they have the disadvantages such as
high cost, complicated and inadequate instrumentation for field
application.
An interesting alternative method for determination of Pb(II)
and other species at trace and ultra-trace levels is stripping vol-
tammetry, especially those involving adsorptive steps [8–10]. This
is one of the most accessible and widely used techniques [11]
characterized by a remarkable sensitivity, low cost, simple equip-
ment, rapid analysis and the possibility of analyses in colored
samples or with dispersed solid particles [12]. Regarding electrode
materials, mercury has been widely used in stripping analysis of
lead due to its ability of yield amalgam with the analyte, wide
potential window, high sensitivity and reproducibility [13,14].
High toxicity, difficulties with storage and disposal of mercury has
stimulated the research for other materials with similar electro-
analytical characteristics and low toxicity [15–17].
Bismuth modified electrodes provided an alternative material
for electrochemical stripping analysis. This metal was introduced
by Wang and coworkers in 2000 [18] and it has excellent chemical
and electrochemical characteristics such as low toxicity, ability to
form alloys with different metals, wide potential ranges and low
sensitivity to dissolved oxygen [19]. Bismuth modified electrodes

http://dx.doi.org/10.1016/j.talanta.2015.04.052
0039-9140/& 2015 Published by Elsevier B.V.
222 D. Agustini et al. / Talanta 142 (2015) 221–227
are usually built on different substrates: gold, platinum, glassy
carbon, screen-printed ink, carbon fiber or carbon pastes [20]. The
latter has been widely used due to its inexpensive and easy pre-
paration, renewable surface and stability in different solvents [21].
The most common procedures used for preparing bismuth-film
modified electrodes are the in situ [22] or ex situ [23,24]. Some
other procedures include carbon paste containing bismuth pre-
cursor or powder such as the incorporation of Bi2O3 with sub-
sequent reduction to metallic bismuth [25]. In the last years, the
electrode modification with bismuth nanostructures has been
proposed to combine the electrochemical bismuth characteristics
with the inherent advantages of nanomaterials such as enhanced
mass transport, high surface area and improved signal-to-noise
ratio [26,27]. However, the fabrication of nano-bismuth is char-
acterized for complicated synthesis, complex instrumentation or
long time reduction [28–30]. An alternative route for simple and
rapid construction of bismuth nanostructures at an electrode
surface could be achieved by using functionalized materials to
support the bismuth ions before the electrochemical reduction.
Biochar is a kind of carbonaceous material easily obtained by
thermal degradation (pyrolysis) of biomass (such as crop residues,
wood scraps, municipal and industrial solid waste and animal
manure) in the absence of air [31]. The production of biochar can
be considered as low-cost and environmental friendly and its
applications include soil amendment, power source conversion
processes, carbon sequestration and as sorbent material for the
removal of organic and inorganic contaminants in soil and water
[32–34]. In these works, biochar has exhibited high removal
capacity, especially for metallic ions, in a relatively short time
when compared with other sorbent materials. This adsorption
capacity of biochar was exploited in electrochemical stripping
measurements only in two works previously reported by Sugui-
hiro et al. [35] for Pb(II) and Cd(II) determination in water samples
and Oliveira et al. [36] for Cu (II) determination on spirit drinks. Its
use as platform for growth of metallic nanostructures has not been
explored yet.
In this paper, we report for the first time the development of
easy and sensitive nBi-BchCPE for in-field pre-concentration and
fast quantification of Pb(II) by differential pulse adsorptive stripping
voltammetry (DPAdSV). The main novelty of this work is the use of
biochar simultaneously as platform for growth of Bi nanostructures
as well as spontaneous pre-concentration and subsequent deter-
mination of Pb(II) ions. Under these conditions, Pb(II) ions can be
pre-concentrated simultaneously using different electrodes (as
passive samplers) which make possible rapid and consecutive
measurements. The proposed sensor has shown a synergic effect
based on the high adsorption capacity of biochar for Bi(III) and Pb
(II) ions and the enhancement of the electrochemical response
characterized by presence of Bi nanostructures on the electrode
surface. The proposed electrode was applied for trace determination
of Pb(II) released from overglaze-decorated ceramic dishes samples
and the results were compared with ICP-OES.
2. Experimental
2.1. Material and reagents
The biochar (with a particle size of 80 meshes) was produced
from castor oil cake by pyrolysis at 300 °C with a heating rate of
10 °C/min (60 min of residence time). All chemicals had analytical
reagent grade and used without further purification. The solutions
were prepared with purified water in a Millipore Milli-Q system. A
standard solution containing 1000 mg L
1 Pb(II) (Merck) was used
as stock. Solutions containing different concentrations of Pb(II) ions
were made by dilution in water. Bi(III) ion solution (3.0 mmol L
1)
was prepared by dissolving Bi(NO3)3  5H2O in 0.04 mol L
1 HNO3.
Acetate buffer solutions (0.01 mol L
1) were made by mixing
appropriated volumes of 0.05 mol L
1 sodium acetate solution with
0.05 mol L
1 acetic acid solution; the required pH was adjusted
with a sodium hydroxide solution. Potassium nitrate solution
(0.1 mol L
1) was prepared by dilution of KNO3 in purified water.
2.2. Apparatus
Voltammetric measurements were performed in a mAUTOLAB
Type III (Metrohm) connected to a microcomputer controlled by
software (NOVA 1.7) for data acquisition and instrumental control.
All electrochemical experiments were carried out in a three-elec-
trode configuration employing a nBi-BchCPE as the working
electrode, platinum wire as counter electrode and Ag/AgCl
(3.0 mol L
1 KCl) as reference electrode. All the experiments were
performed in a 25 mL glass cell at room temperature and without
removing oxygen.
A Metrohm 780 pH meter was used to determine the pH of
solutions. Scanning Electron Microscopy (SEM) images were
obtained from a Quanta 450 ESEM FEG and Energy Dispersive
X-ray Spectroscopy (EDS) analysis was performed from an EDAX
microanalysis. For the ICP-OES Pb(II) measurements a Thermo
Scientific, model 6000 Series equipment was used.
2.3. Preparation of the modified carbon paste electrode
The carbon paste electrode modified with biochar (BchCPE)
was prepared by carefully mixing the dispersed graphite powder
(45–75% (w/w)) (Fischer) with biochar (0–30% (w/w)) and mineral
oil (25% (w/w)). The components were mixed manually in a
mortar and pestle for at least 10 min to obtain an appropriate
homogenization. Subsequently, the modified carbon paste was
packed into piston-driven electrode holder (PVC cylindrical tube,
i.d. 3.0 mm) and arranged with a copper wire serving as an
external electric contact. The electrode surface was smoothed by
polishing on a piece of paper. For the carbon paste electrode
modified with biochar and bismuth nanostructures (nBi-BchCPE)
preparation, the carbon paste electrode modified only with bio-
char (BchCPE) was placed in 10 mL of Bi(III) ions solution for 30 s
under no applied potential and stirring conditions.
2.4. Measurement procedure
The voltammetric measurements were performed by adsorp-
tive stripping voltammetry. For pre-concentration step, the nBi-
BchCPE was immersed in a stirred 10 mL of 0.01 mol L
1 acetate
buffer solution (pH 6) containing Pb(II) for 5 min at open circuit
potential. The electrode was then removed from the pre-con-
centration cell, gently rinsed with 0.01 mol L
1 acetate buffer,
placed in the electrochemical cell containing 10 mL of a quiescent
supporting electrolyte (0.01 mol L
1 acetate buffer pH 4.5 and
0.1 mol L
1 KNO3) and applied a potential of
0.8 V (vs. Ag/AgCl,
KCl 3.0 mol L
1) for 30 s. After that, the voltammograms were
recorded by applying a potential scan from
0.8 to þ0.5 V under
differential pulse voltammetry conditions with potential ampli-
tude of 100 mV, pulse time of 25 ms and step potential of 5 mV.
Finally, the electrode surface was renewed by mechanical polish-
ing in paper.
2.5. Analysis of real samples
The leaching of Pb(II) present in these dishes was performed
according to methodology adapted from ANVISA [37]. For the
release test, 0.1 mol L
1 acetic acid solution was used for 2 h at a
temperature of 80 °C. An aliquot of the resulting solution was
 D. Agustini et al. / Talanta 142 (2015) 221–227
added to the pre-concentration solution so that the concentration
of Pb(II) stays within the linear range of techniques. Six brands of
Chinese (porcelain/ceramic) dishes were evaluated with the
techniques of DPAdSV (using the nBi-BchCPE) and ICP-OES.
3. Results and discussion
3.1. Voltammetric performance of Bi-BchCPE for Pb(II) determination
The addition of the modifiers (biochar and bismuth) in the car-
bon paste aims to improve the adsorption and, consequently, the
detectability of Pb(II). To evaluate the effect of the modifiers in the
voltammetric response, the CPE, BchCPE and Bi-BchCPE were sub-
mitted to measurements after pre-concentration step in solution
containing a 10 mmol L
1 of Pb(II) ions. In Fig. 1A, the CPE presented
a very low adsorption capacity and negligible response. However,
the signal observed for lead oxidation (Epa ¼
0.57 V) using the
BchCPE (Fig. 1B) is remarkably higher than CPE which can be
attributed to the presence of biochar in the paste due to the phe-
nomena such as metal exchange, complexation with functional
groups, surface precipitation or physical adsorption that can sig-
nificantly increase the pre-concentration of Pb(II) on the electrode
surface [38]. Finally Fig. 1C represents the peak current of Pb(II) in
Bi-BchCPE being remarkably greater than BchCPE, which clearly
confirms the efficiency in the use of proposed sensor to the deter-
mination of Pb(II) due to the inherent advantages of the bismuth.
Bismuth oxidation can be observed at potential of
0.10 V.
3.2. SEM and EDS characterization of modified carbon paste
electrodes
The size and distribution of bismuth anchored on the BchCPE
can affect significantly the determination of Pb(II). Fig. 2A shows a
homogeneous dispersion of bismuth nanostructures (light gray
spherical nanodots with some white agglomerates) on the biochar
particles incorporated on the electrode surface which can be
observed in detail in Fig. 2B. Fig. 2C shows the size distribution
graph obtained by manual counting of at least 500 structures,
which indicates an average size of 4273 nm. The obtained bis-
muth nanostructures were manufactured and deposited on the
electrode surface by using an easier strategy in comparison with
some other reported [22].
To investigate the interaction between biochar, bismuth and lead,
EDS measurements were performed in BchCPE and nBi-BchCPE before
Fig. 1. DPAdSV of 1.0  10
5 mol L
1 Pb(II) at (A) CPE, (B) BchCPE and (C) Bi-
BchCPE in 0.01 mol L
1 acetate buffer pH 4.5 þ 0.1 mol L
1 KNO3. Reduction
potential:
0.8 V, reduction time: 30 s, potential scan:
0.8 to þ0.5 V, potential
amplitude: 100 mV, pulse time: 25 ms, step potential: 5 mV. Pre-concentration step
in 0.01 mol L
1 acetate buffer pH 6 containing 10 mmol L
1 of Pb(II) ions for 5 min.
223
and after pre-concentration in solution containing 10 mmol L
1 of Pb
(II) ions. Individual determination of lead and bismuth was necessary
to investigate the less intense peaks of the layers Lα and Lβ for these
metals in order to avoid signal overlap. A good separation of these
layers were obtained, with values of 10.51; 10.80; 12.56 and 12.97 keV
to Pb Lα, Bi Lα, Pb Lβ and Bi Lβ respectively. As can be seen in Fig. 2D,
the BchCPE (Fig. 2D-Curve I) before pre-concentration of lead, the EDS
spectrum has not indicated the presence of any element which could
interfere with the identification of bismuth or lead. After pre-con-
centration of Pb(II) in BchCPE (Fig. 2D-Curve II), it was possible to
observe the characteristic peaks of Pb Lα (10.51 keV) and Pb Lβ
(12.56 keV). For nBi-BchCPE (Fig. 2D-Curve III), before the pre-con-
centration of lead, it was noted peaks of Bi Lα (10.80 keV) and Bi Lβ
(12.97 keV) confirming the incorporation of bismuth in the biochar.
Finally, for nBi-BchCPE after pre-concentration and reduction of Pb(II)
(Fig. 2D-Curve IV) the EDS spectrum taken from a nanodot has
revealed the presence of both Bi and Pb in the same nanostructure.
These results confirm not only the pre-concentration of analyte at the
electrode surface but also they suggest strongly the formation of alloy
between lead with bismuth.
3.3. Influence of experimental parameters on the voltammetric
response nBi-BchCPE
In order to obtain the best voltammetric behavior of the nBi-
BchCPE for Pb(II) determination, several parameters related to paste
composition, bismuth incorporation, pre-concentration solution and
operational parameters were examined in detail.
The amount of biochar added in the nBi-BchCPE has a sig-
nificative influence on the voltammetric responses. Electrodes
with different percentages of biochar were prepared and exam-
ined for their voltammetric signals to Pb(II) under identical con-
ditions. The peak currents for Pb(II) have increased with increasing
the amount of biochar in the nBi-BchCPE due to the increased
adsorption capacity of the electrode. At 25% (w/w) of biochar the
highest peak current was obtained. For amounts of biochar higher
than 25% the response of the nBi-BchCPE decreased due to the
reduction in conductivity of the modified electrode [39]. According
to these results a carbon paste composition of 25% biochar, 50%
graphite and 25% mineral oil was used in further studies.
The presence of bismuth nanostructures on the electrode surface
is fundamental to its high sensitivity to the determination of Pb(II).
For a fast and stable incorporation of nano-bismuth the pH of the
solution has great influence. In this way, pH solutions ranging from
0.5 to 2.0 were used to study the grafting of Bi(III) ions on the
electrode surface. The maximum incorporation was achieved at pH
1.5, whereas at low pH values a strong competition occurred
between Bi(III) and H þ ions for adsorption sites of biochar. At pH
above 1.5, there is a spontaneous process of hydrolysis of bismuth
ions according to the reaction [40] Bi3 þ þ3H2O⇆Bi(OH)3 þ3H þ ,
limiting the use of adsorption solutions of Bi(III) at pH values
around 1.5.
The effect of the amount of bismuth added on the biochar was
evaluated by immersion of the electrode in the solution containing
bismuth ions for different intervals of time ranging from 15 to
300 s. After that, the electrode was submitted to pre-concentration
step in solution containing 10 mmol L
1 of Pb(II). As shown in
Fig. 3, the faradaic signals observed for oxidation of bismuth have
increased with increase of time suggesting an increase in the
amount Bi(III) ions incorporated on the electrode surface. By other
side, the stripping peak height of Pb(II) (Fig. 3) increased with
increasing time of Bi(III) grafting from 15 to 30 s and it gradually
decreases for values above 30 s probably due to the formation of
large clusters of nano-bismuth with consequent saturation of
adsorption sites of biochar. Therefore, the optimum time for Bi(III)
224 D. Agustini et al. / Talanta 142 (2015) 221–227
Fig. 2. (A) SEM micrograph of nBi-BchCPE with magnification of 25k  . (B) Detail of bismuth nanostructures in 132k  . (C) Size distribution graph of bismuth nanos-
tructures. (D) EDX pattern of BchCPE and nBi-BchCPE before and after Pb(II) pre-concentration.
Fig. 3. Effect of time of incorporation of Bi(III) ions on the anodic peaks (n¼ 3)
current for bismuth and lead oxidation. Pre-concentration step in 0.01 mol L
1
acetate buffer pH 6 containing 10 mmol L
1 of Pb(II) ions for 5 min (n ¼3).
incorporation was 30 s, which was chosen for following further
experiments.
The adsorption of Pb(II) on the surface of nBi-BchCPE occurs in
the pre-concentration solution and for efficient adsorption lead
ions must be in their ionic free form. So the effect of pH for pre-
concentration of Pb(II) at the electrode surface was investigated in
the range of 3.0–8.0. It was found that the peak current of Pb(II)
increased with increasing pH reaching a maximum at pH value of
6.0 and progressively decreased at higher pH values. At low pH
values competition occurs between Pb(II) and H þ ions for the
adsorption sites on the electrode. For high pH values, the low
response can be ascribed to the hydrolysis of lead [41,42]. There-
fore, the following experiments were carried out in pre-con-
centration solution with pH 6.0.
To evaluate the dependence between peak current and pre-
concentration time, Pb(II) ions were accumulated on the nBi-BchCPE
using pre-concentration time varying from 1 to 30 min. Anodic peak
currents for Pb(II) have increased as the time pre-concentration
increases indicating a progressive increase in the amount of Pb(II)
adsorbed on the electrode. The peak currents start to stabilize after
15 min of pre-concentration due to the equilibrium between ions in
solution and those adsorbed on the electrode surface. For further
studies, an accumulation time of 5 min was used in order to find a
better combination between sensitivity and time of analysis.
In order to evaluate the effect of the composition of supporting
electrolyte in the voltammetric signal of Pb(II), phosphate buffer
and acetate buffer solutions (both at pH 4.5) were studied. The
best response was reached with measurements using acetate
buffer solutions due to the low tendency of formation of stable
acetate-complexes with Pb(II) being indicated by the stability
constants for [Pb(Ac)] þ and [Pb(Ac)2], which are reported as
log K ¼2.68 and log K ¼4.08, respectively. These constants are
significatively lower than phosphate-Pb(II) species [PbHPO4] and
[PbH2PO4] þ , which have stability constants of log K ¼15.48 and
log K ¼21.07, respectively [43]. The influence of acetate buffer
concentration was studied in the range of 0.01–0.5 mol L
1 at pH
4.5 (controlled ionic strength). Maximum peak current was
obtained at 0.01 mol L
1 and a progressive decrease for higher
concentrations of acetate buffer solution was observed. Thus, a
supporting electrolyte consisting of 0.01 mol L
1 acetate buffer
and 0.1 mol L
1 of KNO3 was selected for further studies.
The effect of pH of supporting electrolyte on the voltammetric
responses of Pb(II) was also studied for pH values between 2.0 and
7.0. Maximum peak current was obtained at pH 4.5. At lower pH
values the reduction in the magnitudes of voltammetric signal can
be attributed to replacement of Pb(II) pre-concentrated on the
electrode surface by H þ ions. For these reasons, the optimum pH
of 4.5 was selected for following experiments.
Beyond the general characteristics of the system above men-
tioned, instrumental parameters can affect significantly the elec-
trode response.The effect of the reduction potential was studied in
the range of
1.3 V to
0.6 V to the stripping peak heights of Pb
(II). The best result was obtained at
0.8 V since in more positive
potential values the reduction of Pb(II) become incomplete due to
the proximity of the redox potential of lead. For potential values
 D. Agustini et al. / Talanta 142 (2015) 221–227 225

more negative than
0.8 V there was a gradual and slight inter- 25 ms and potential amplitude of 100 mV) was selected for ana-
ference of H þ ions in the reduction of lead. Reduction time applied lytical applications.
before voltammetric scan was investigated in the range of 0–120 s In order to improve the analytical performance of the proposed
and it has demonstrated a gradual increase in the response sensor calibration curves were constructed using the pre-con-
between 0 and 30 s, followed by stabilization of current values centration time of 20 min under DPV conditions (Fig. 4A and B).
over this time indicating that 30 s is enough for the effective Fig. 4C shows a calibration plot that was linear over the range
reduction of Pb(II) ions previously adsorbed. Based on these concentration from 5.0 to 1000 nmol L
1 for Pb(II). The linear
results, a reduction potential of
0.8 V for 30 s was selected for regression equation found was I (μA)¼
1.27 þ82.02CPb(II) (where
further optimization studies. CPb(II) in mmol L
1). The LOD obtained was 1.41 nmol L
1 and the
LOQ was 4.70 nmol L
1.
3.4. Analytical performance of nBi-BchCPE In comparison with a previously described Pb(II) sensor with
biochar in the absence of bismuth [35] the proposed sensor
In order to obtain the best analytical performance for the reaches a limit of detection (LOD) almost 10-fold better. The ana-
proposed sensor, calibration curves for Pb(II) were obtained by lytical features of the proposed electrode were compared (Table 2)
using of DPV, SWV and LSV under optimal conditions (not shown). with other bismuth modified electrodes previously reported in the
Table 1 shows the figures of merit of nBi-BchCPE for each vol- literature for Pb(II) determination. Moreover, the main advantage
tammetric technique used; the limit of detection (LOD) was esti- of the proposed sensor is the Pb(II) pre-concentration performed
mated based on three times the blank standard deviation divided at open circuit potential conditions that allows its use as a passive
by slope of the calibration curve and the limit of quantification sampler (especially for environmental applications) as well as the
(LOQ) was calculated based on 10 times the blank standard
deviation divided by slope of the calibration curve. Table 2
Calibration curves obtained using DPV have shown a linear Comparison of present work and other bismuth modified electrodes for the
determination of Pb(II).
response for a wider concentration range of Pb(II) ions in com-
parison with other voltammetric techniques evaluated. From Electrode Technique LOD Linear range Ref.
Table 1, it was observed that LSV had the poorer analytical per- (nmol L
1) (nmol L
1)
formance probably due to the high capacitive current present in
m-NP/BiFE DPAdSV 87 482.6–1930.5 [44]
their measurements, which resulted in a low sensitivity and BiFE SWASV 33 50–482.6 [45]
high LOD and LOQ. The SWV showed the best sensitivity Bi-HA CME SWASV 24 50–965.3 [46]
(151.64 mA L mmol
1) and an elevated noise in the background Bi/poly(p-ABSA) DPASV 3.7 5–627.4 [47]
current. For these reasons, considering the best LOD and LOQ, DPV film electrode
Bismuth modified SWASV 9.6 50–2413.1 [48]
(under optimized conditions: step potential of 5 mV, pulse time of carbon tape
electrode
Table 1 BiFE SWASV 2.9 5–241.3 [49]
Analytical performance for Pb(II) determination by DPV, SWV and LSV using the Bi-CNT electrode SWASV 6.3 9.6–482.6 [50]
proposed sensor. nBi-BchDCPE DPAdSV 1.4 5–1000 This
work
DPV SWV LSV
m-NP/BiFE: micro/nanoparticle bismuth film electrode; DPAdSV: differential pulse
Linear range (nmol L
1) 10–5000 50–1000 500–10,000 adsorptive stripping voltammetry; BiFE: bismuth film electrode; SWASV: square
Sensitivity (mA L mmol
1) 29.61 151.64 3.80 wave anodic stripping voltammetry; Bi-HA CME: bismuth-modified hydroxyapatite
Correlation coefficient 0.9997 0.9991 0.9995 carbon electrode; Bi/poly(p-ABSA) film electrode: bismuth/poly(p-aminobenzene
Limit of detection-LOD (nmol L
1) 2.83 7.00 149 sulfonic acid) film electrode; Bi-CNT electrode: bismuth-modified carbon nanotube
Limit of quantification-LOQ (nmol L
1) 9.43 23.3 495 electrode; nBi-BchDCPE: nano-bismuth modified biochar doped carbon paste
electrode.

100
80
12
75
60

10
50 40
I /µA

Iap /µA
I /µA

8 20
25

0
0 6
-0.8 -0.6 -0.4 -0.8 -0.6 -0.4 0.0 0.5 1.0
-1
E / V vs. Ag/AgCl KCl 3 mol L -1
CPb2+ /µmol L
Fig. 4. DPV measurements under optimized conditions for Pb(II) using nBi-BchCPE. (A) Pb(II) concentration ranging from 0 to 1.0 mmol L
1; Pb(II) concentration ranging
from 0 to 0.1 mmol L
1; (C) calibration plot (n¼ 3).
226 D. Agustini et al. / Talanta 142 (2015) 221–227
Fig. 5. Correlation plot for analyzed samples using results obtained by the
proposed sensor and those provided by ICP-OES methodology.
possibility of rapid consecutive measurements after pre-con-
centration step.
The intra-day reproducibility study of the nBi-BchCPE was
carried out based on the DPV response to 10 mmol L
1 Pb(II) pre-
concentrated for 5 min using 5 different electrode surfaces. The
relative standard deviation (RSD) found was 3.40%, demonstrating
good reproducibility of the nBi-BchCPE, which can be attributed to
a good control of the carbon paste preparation and modification
with biochar and bismuth. For inter-day reproducibility study the
same experiment was repeated for five consecutive days indicat-
ing a RSD o5.0%.
3.5. Effect of concomitants species
The influence of ionic species on the voltammetric responses
was examined using solution containing Pb(II) ions (concentration
fixed at 2.40 mmol L
1) and foreign ionic species at concentration
levels based on limit established by CONAMA (Brazilian legisla-
tion) [51]. The evaluated species were considered as an interfering
agent when the electrochemical signal for Pb(II) exhibited a
deviation more than 75.0%. It was observed that the presence of
species Ag þ , As3 þ , Ba2 þ , Cd2 þ , Cl
, Cr3 þ , Cr6 þ , F
, Hg2 þ , Mn2 þ ,
Ni2 þ , NO−3 , Se4 þ , SO2−
4 and Zn
2þ
had no interference in the vol-
tammetric response of Pb(II) even at high concentration level. A
significant decrease in peak currents for Pb(II) was observed when
Cu2 þ (10-fold), Fe3 þ (100-fold) and Sn2 þ (15-fold) were present in
the pre-concentration solution indicating that these metal ions
compete with Pb(II) for the binding sites of biochar. However,
interference effect observed is constant and it could be minimized
by using the standard addition procedure.
3.6. Analyses in real samples
The nBi-BchCPE was applied to the analysis of Pb(II) released
from overglaze-decorated ceramic dishes. The solution used in the
release test (0.1 mol L
1 acetic acid) was added directly to the pre-
concentration solution without any sample pre-treatment. Con-
centrations of lead ions were determined by the standard addition
method and the voltammetric results obtained were validated
using ICP-OES. Fig. 5 presents the Pb(II) concentrations measured
by the proposed electrode and corresponding ICP-OES results. A
good agreement was found between the values obtained by nBi-
BchCPE and ICP-OES, with deviations less than 5.0%. Linear
regression obtained from Fig. 5 has given a value of R¼ 0.99941, a
slope of 0.99475 and an intercept with a value of 0.12561. In
addition, the paired t-test (99% confidence level and 5 degrees of
freedom) indicate that there are no significant differences between
the results obtained by the two methods. Therefore, these results
demonstrate that the proposed electrode can be successfully
applied in the determination of Pb(II) in real samples.
4. Conclusions
The incorporation of bismuth nanostructures on the biochar
allowed the development of a new modified carbon paste electrode,
which has exhibited detection limits of nmol L
1 for Pb(II) due to
the high adsorptive capacity of biochar coupled with electro-
chemical advantages of bismuth in nanoscale. It was also observed
that the proposed electrode had a linear response for a wide range
of Pb(II) concentration, excellent reproducibility and few interfering
ions. Thus, the main features of nBi-BchCPE are low cost, ease of
fabrication, able to portability (due to pre-concentration step in
open circuit), quickness and high sensitivity in the analyses. Finally,
the analyses of Pb(II) released from overglaze-decorated ceramic
dishes without any sample pre-treatment proved the efficiency of
the proposed electrode and showed its potential for fast, easy and
sensitive monitoring in various samples.
Acknowledgments
We gratefully acknowledge financial support from Brazilian
foundations: Fundação Araucária, CAPES, and CNPq.
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