Author’s Accepted Manuscript

Sensitive voltammetric determination of lead

released from ceramic dishes by using of bismuth
nanostructures anchored on biochar

Deonir Agustini, Antonio Salvio Mangrich, Márcio

F. Bergamini, Luiz Humberto Marcolino-Junior
www.elsevier.com/locate/talanta

PII: S0039-9140(15)00301-X
DOI: http://dx.doi.org/10.1016/j.talanta.2015.04.052
Reference: TAL15552
To appear in: Talanta
Received date: 15 March 2015
Revised date: 16 April 2015
Accepted date: 17 April 2015
Cite this article as: Deonir Agustini, Antonio Salvio Mangrich, Márcio F.
Bergamini and Luiz Humberto Marcolino-Junior, Sensitive voltammetric
determination of lead released from ceramic dishes by using of bismuth
nanostructures anchored on biochar, Talanta,
http://dx.doi.org/10.1016/j.talanta.2015.04.052
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 Sensitive voltammetric determination of lead released from ceramic

dishes by using of bismuth nanostructures anchored on biochar

Deonir Agustinia, Antonio Salvio Mangrichb,c, Márcio F. Bergaminia, Luiz Humberto

Marcolino-Juniora*

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

E&A/CNPq), Brazil.

*email address: luiz1berto@ufpr.br

Telephone number: +55 41 3361-3177

Fax number: +55 41 3361-3186

Abstract

A simple and sensitive electroanalytical method was developed for determination of

nanomolar levels of Pb(II) based on the voltammetric stripping response at a carbon

paste electrode modified with biochar (a special charcoal) and bismuth nanostructures

(nBi-BchCPE). The proposed methodology was based on spontaneous interactions

between the highly functionalized biochar surface and Pb(II) ions followed by 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-concentration, reduction of accumulated lead ions at the

electrode surface and stripping step under differential pulse voltammetric conditions

(DPAdSV). SEM images revealed dimensions of bismuth nanodots ranging from 20 nm

to 70 nm. The effects of main parameters related to biochar, bismuth and operational

parameters were examined in detail. Under the optimal conditions, the proposed

sensor has exhibited linear range from 5.0 to 1,000 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-decorated ceramic dishes. Results obtained were

compared with those given by inductively coupled plasma optical emission

spectroscopy (ICP-OES) and they are in agreement at a 99% of confidence level.

Keywords: Bismuth nanostructures; Electrochemical Sensor; Lead; Ceramic dishes.

1. Introduction

Lead is one of the most useful metals used since ancient civilizations 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 nervous systems

[2], lag in learning and low neurological development in children [3]. Although several

efforts have been made to reduce the exposure to this metal, a large number of people

continue 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 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 voltammetry, specially those invoving

adsorptive steps [8-10]. This is one of the most accessible and widely used techniques

[11] characterized by a remarkable sensitivity, low cost, simple equipment, 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 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 electroanalytical characteristics and low toxicity [15-17].

Bismuth modified electrodes provided an alternative material for

electrochemical stripping analysis. This metal was introduced by Wang with coworkers

1
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 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 its inexpensive and easy

preparation, 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 including

carbon paste containing bismuth precursor or powder such as the incorporation of

Bi2O3 with subsequent reduction to metallic bismuth [25]. In the last years, the

electrode modification with bismuth nanostructures have 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 characterized

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 achivied by using of 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 Suguihiro et al. [35]

2
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 determination 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 per minute (60 minutes 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

3
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 µAUTOLAB 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-electrode 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 were 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

4
with biochar (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 adsorptive 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 minutes at open

circuit potential. The electrode was then removed from the pre-concentration 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 +0.5 V under differential pulse voltammetry conditions with potential

amplitude of 100 mV, pulse time of 25 ms and step potential of 5 mV. Finally, the

electrode surface was renewed by mechanical polishing 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, it was used 0.1 mol L-1

acetic acid solution for 2 hours at a temperature of 80°C. An aliquot of the resulting

solution was 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

5
 The addition of the modifiers (biochar and bismuth) in the carbon 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 submitted to measurements after pre-concentration step in solution containing a

10 µmol 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 = - 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 phenomena such as metal exchange,

complexation with functional groups, surface precipitation or physical adsorption that

can significantly increases the pre-concentration of Pb(II) on the electrode surface [38].

Finally the 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 determination of Pb(II) due to the inherent advantages of the

bismuth. Bismuth oxidation can be observed at potential of -0.10 V.

Fig. 1

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 42±3 nm. The

obtained bismuth 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 and after pre-

concentration in solution containing 10 µmol L-1 of Pb(II) ions. For individual

6
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, PbLβ 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-concentration 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-concentration 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.

Fig. 2

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 compositon, bismuth incorporation,

pre-concentration solution and operational parameters were examined in detail.

The amount of biochar added in the nBi-BchCPE has a significative influence

on the voltammetric responses. Electrodes with different percentages of biochar were

prepared and examined for their voltammetric signals to Pb(II) under identical

conditions. 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 the reduction in

7
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 competion occurred between Bi(III) and H+ 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+ + 3H2O D Bi(OH)3 + 3H+, 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 of 10 µmol L-1 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 by formation of large clusters of nano-bismuth with consequent saturation of

adsorption sites of biochar. Therefore, the optimum time for Bi(III) incorporation was 30

s, which was chosen for following further experiments.

Fig. 3

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 to 8.0. It was found that the peak current of Pb(II)

8
increased with increasing the pH reaching a maximum at pH value of 6.0 and

progressively decreased at higher pH values. At low pH values occurs the competition

between Pb(II) and H+ 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]. Therefore,

the following experiments were carried out in pre-concentration 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 minutes. 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 minutes 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 minutes 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)]+ and [Pb(Ac)2], which are

reported as logK=2,68 and logK=4,08, respectively. These constants are significatively

lower than phosphate-Pb(II) species [PbHPO4] and [PbH2PO4]+, which have stability

constants of logK=15.48 and logK=21.07, respectively [40]. The influence of acetate

buffer concentration was studied in the range of 0.01 to 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

9
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+ ions. For these reasons, the optimum pH of 4.5 was selected for

following experiments.

Beyond the general characteristics of the system above mentioned,

instrumental parameters can affect significantly the electrode 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 more negative than -0.8 V there was a

gradual and slight interference of H+ ions in the reduction of lead. Reduction time

applied before voltammetric scan was investigated in the range of 0–120 s and it has

demonstrated a gradual increase in the response between 0 and 30 seconds, followed

by stabilization of current values over this time indicating that 30 s are enough for the

effective reduction of Pb(II) ions previously adsorbed. Based on these results, a

reduction potential of −0.8 V for 30 s was selected for further optimization studies.

3.4. Analytical performance of nBi-BchCPE

In order to obtain the best analytical performance for the proposed sensor,

calibration curves for Pb(II) were obtained by using of DPV, SWV and LSV under

optimal conditions (not shown). Table 1 shows the figures of merit of nBi-BchCPE for

each voltammetric technique used; the limit of detection (LOD) was estimated based

on three times the blank standard deviation divided by slope of the calibration curve

and the limit of quantification (LOQ) was calculated based on ten times the blank

standard deviation divided by slope of the calibration curve.

Table 1

Calibration curves obtained using DPV have shown a linear response for a

wider concentration range of Pb(II) ions in comparison with other voltammetric

10
techniques evaluated. From Table 1, it was observed that LSV had the poorer

analytical performance probably due to the high capacitive current present in their

measurements, which resulted in a low sensitivity and high LOD and LOQ. The SWV

showed the best sensitivity (151.64 µA L µmol-1) and an elevated noise in the

background current. For these reasons, considering the best LOD and LOQ, DPV

(under optimized conditions: step potential of 5 mV, pulse time of 25 ms and potential

amplitude of 100 mV) was selected for analytical applications.

In order to improve the analytical performance of the proposed sensor

calibration curves were constructed using pre-concentration time of 20 minutes under

DPV conditions (Fig. 4A and 4B). Fig. 4C shows a calibration plot that was linear over

the range concentration from 5.0 to 1,000 nmol L-1 for Pb(II). The linear regression

equation found was I (μA) = -1.27 + 82,02CPb(II) (where CPb(II) in µmol L-1). The LOD

obtained was 1.41 nmol L-1 and the LOQ was 4.70 nmol L-1.

Fig. 4

In comparison with a previously described Pb(II) sensor with biochar in the

absence of bismuth [35] the proposed sensor reaches a limit of detection (LOD) almost

10-fold better. The analytical features of the proposed electrode were compared (Table

2) with other bismuth modified electrodes previously reported in the literature for Pb(II)

determination. Moreover, the main advantage of the proposed sensor is the Pb(II) pre-

concentration performed at open circuit potential conditions that allows its use as a

passive sampler (especially for environmental applications) as well as the possibility of

rapid consecutive measurements after pre-concentration step.

Table 2

The intra-day reproducibility study of the nBi-BchCPE was carried out based on

the DPV response to 10 µmol L-1 Pb(II) pre-concentrated for 5 minutes 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

11
bismuth. For inter-day reproducibility study the same experiment was repeated by five

consecutive days indicating a RSD < 5.0%.

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 µmol L-1) and foreign

ionic species at concentration levels based on limit established by CONAMA (Brazilian

legislation) [51].The evaluated species were considered as interfering agent when the

electrochemical signal for Pb(II) exhibited a deviation more than ±5.0%. It was

observed that the presence of species Ag+, As3+, Ba2+, Cd2+, Cl-, Cr3+, Cr6+, F-, Hg2+,

Mn2+, Ni2+, NO3-, Se4+, SO42- and Zn2+ had no interference in the voltammetric response

of Pb(II) even at high concentration level. A significant decrease in peak currents for

Pb(II) was observed when Cu2+ (10-fold), Fe3+(100-fold) and Sn2+(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 of 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.

Concentrations of lead ions were determined by 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 the 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 the Fig.5 has given a value of R = 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

12
degrees of freedom) indicates 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.

Fig. 5

4. Conclusions

The incorporation of bismuth nanostructures on 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

electrochemical advantages of bismuth in nanoscale. It was also observed that the

proposed electrode had a linear reponse 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 of Pb(II) in various samples.

Acknowledgements

We gratefully acknowledge financial support from Brazilian foundations:

Fundação Araucária, CAPES, and CNPq.

13
References

[1] J. F. Quintana, F. Arduinia, A. Aminec, F. Punzod, G. L. Destri, C. Bianchini, D.

Zane, A. Curulli, G. Palleschi, D. Moscone, Part I: A comparative study of bismuth-

modified screen-printed electrodes for lead detection, Anal. Chim. Acta 707 (2011)

171–177.

[2] D. A. Gidlow, Lead toxicity, Occup. Med. 54 (2004) 76-81.

[3] N. C. Papanikolaou, E. G. Hatzidaki, S. Belivanis, G. N. Tzanakakis, A. M.

Tsatsakis, Lead toxicity update. A brief review, Med. Sci. Monit.11 (2005) 329-336.

[4] L. Patrick, Lead toxicity, a review of the literature. Part. I: Exposure, evaluation, and

treatment, Alt. Med. Rev. 11 (2006) 1-22.

[5] M. G. Korn, J. B. Andrade, D. S. Jesus, V. A. Lemos, M. L. S. F. Bandeira, W. N. L.

Santos, M. A. Bezerra, F. A. C. Amorim, A. S. Souza, S. L. C. Ferreira, Separation and

pre concentration procedures for the determination of lead using spectrometric

techniques: A review, Talanta 69 (2006) 16-24.

[6] N. Zhang, H. Peng, S. Wang, B. Hu, Fast and selective magnetic solid phase

extraction of trace Cd, Mn and Pb in environmental and biological samples and their

determination by ICP-MS, Microchim. Acta 175 (2011) 121-128.

[7] V. A. Lemos, A. L. Carvalho, Determination of cadiom and lead in human biological

samples by spectrometric techniques: a review, Environ. Monit. Assess. 171 (2010)

255-265.

[8] H. V. Sezgin, H. İ. Gökçel, Y. Dilgin, Adsorptive anodic stripping voltammetric

determination of antimony(III) on a glassy carbon electrode using rivastigmine as a new

chemical receptor, Sens. Actuat. B 209 (2015) 686-694.

[9] K. Hevia, V. Arancibia, C. Rojas-Romo, Levels of copper in sweeteners, sugar, tea,

coffee and mate infusions. Determination by adsorptive stripping voltammetry in the

presence of α-lipoic acid, Microchem. J. 119 (2015) 11-16.

[10] M. Brycht, S. Skrzypek, J. Robak, V. Guzsvány, O. Vajdle, J. Zbiljić,

A. Nosal-Wiercińska, D. Guziejewski, G. Andrijewskia, Ultra trace level determination of

14
fenoxanil by highly sensitive square wave adsorptive stripping voltammetry in real

samples with a renewable silver amalgam film electrode, J. Electroanal. Chem. 738

(2015) 69-76.

[11] A. Economou, Recent developments in on-line electrochemical stripping analysis-

An overview of the last 12 years, Anal. Chim. Acta 683 (2010) 38-51.

[12] E. S. Almeida, E. M. Richter, R. A. A. Munoz, On-site fuel electroanalysis:

Determination of lead, copper and mercury in fuel bioethanol by anodic stripping

voltammetry using screen-printed gold electrodes, Anal. Chim. Acta 837 (2014)38–43.

[13] S. J. R. Prabakar, C. Sakthivel, S. S. Narayanan, Hg(II) immobilized MWCNT

graphite electrode for the anodic stripping voltammetric determination of lead and

cadmium, Talanta 85 (2011) 290-297.

[14] D. Guo, J. Li, J. Yuan, W. Zhou, E. Wang, Nafion film immobilized nano Ag-Hg

amalgam glassy carbon electrode used for simultaneous determination of lead,

cadmium and cupper, Electroanal. 22 (2010) 69-73.

[15] A. Mardegan, S. D. Borgo, P. Scopece, L. M Moretto, S. B. Hocevar, P. Ugo,

Bismuth modified gold nanoelectrode ensemble for stripping voltammetric

determination of lead, Electrochem. Comm. 24 (2012) 28-31.

[16] E. S. Tesarova, L. Baldrianova, M. Stoces, I. Svancara, K. Vytras, S. B. Hocevar,

B. Ogorevc, Antimony powder-modified carbon paste electrode for electrochemical

stripping determination of trace heavy metals, Electrochim. Acta 56 (2011) 6673-6677.

[17] N. Lezia, A. Economou, P. A. Dimovasilis, P. N. Trikalitis, M. I. Prodromidis,

Disposable screen-printed sensors modified with bismuth precursor compounds for the

rapid voltammetric screening of trace Pb(II) and Cd(II), Anal. Chim. Acta 728, (2012) 1–

8.

[18] J. Wang, J. Lu, S. B. Hocevar, P. A. M. Farias, Bismuth-coated carbon electrodes

for anodic stripping voltammetry, Analytical Chemistry 72 (2000) 3218-3222.

[19] J. Wang, Stripping analysis at bismuth electrodes: a review, Electroanal. 17 (2005)

1341-1346.

15
[20] I. Svancara, C. Prior, S. B. Hocevar, J. Wang, A decade with bismuth-based

electrodes in electroanalysis, Electroanal. 22 (2010) 1405-1420.

[21] I. Svancara, K. Vytras, K. Kalcher, A. Walcarius, J. Wang, Carbon paste electrode

in facts, numbers, and notes: A review on the occasion of the 50-years jubilee of

carbon paste in electrochemistry and electroanalysis, Electroanal. 21 (2009) 7-28.

[22] N. Serrano, A. Alberich, J. M. D. Cruz, C. Arinõ, M. Esteban, Coating methods,

modifiers and applications of bismuth screen-printed electrodes, Trends in Anal. Chem.

46 (2013) 15-29.

[23] L. C. S. Figueiredo, B. C. Janegitz, O. Fatibello-Filho, L. H. Marcolino-Junior, C. E.

Banks, Inexpensive and disposable copper mini-sensor modified with bismuth for lead

and cadmium determination using square-wave anodic stripping voltammetry, Anal.

Meth., 5 (2013) 202-207.

[24] P. A. Dimovasilis, M. I. Prodromidis, Bismuth-dispersed xerogel-based composite

films for trace Pb(II) and Cd(II) voltammetric determination, Anal. Chim. Acta769 (2013)

49–55.

[25] A. Economou, Bismuth-film electrodes: recent developments and potentialities for

electroanalysis, Trends in Anal. Chem. 24 (2005) 334-340.

[26] G. J. Lee, C. K. Kim, M. K. Lee, C. K. Rhee, Effect of phase stability degradation of

bismuth on sensor characteristics of nano-bismuth fixed electrode, Talanta 83 (2010)

682-685.

[27] F. W. Campbell, R. G. Compton, The use of nanoparticle in electroanalysis: an

updated review, Anal. and Bioanal. Chem. 396 (2010) 241-259.

[28] L. A. Piankova, N. A. Malakhova, N. Y. Stozhko, K. Z. Brainina, A. M. Murzakaev,

O. R. Timoshenkova, Bismuth nanoparticles in adsorptive stripping voltammetry of

nickel, Electrochem. Comm. 13 (2011) 981-984.

16
[29] A. R. Rajamani, U. B. R. Ragula, N. Kothurkar, M. Rangarajan, Nano- and micro-

hexagons of bismuth on polycrystalline copper: electrodeposition and heavy metal

sensing, Cryst. Eng. Comm. 16 (2014) 2032-2038.

[30] M. A. G. Rico, M. O. Marín, E. P. Gil, Modification of carbon screen-printed

electrodes by adsorption of chemically synthesized Bi nanoparticles for the

voltammetric stripping detection of Zn(II), Cd(II) and Pb(II), Talanta 80 (2009) 631-635.

[31] F. Ronsse, S. Hecke, D. Dickinson, W. Prins, Production and characterization of

slow pyrolysis biochar: influence of feedstock type and pyrolysis conditions, Glob.

Change Biol. Bioenergy 5 (2013) 104-115.

[32] J. Lehmann, M. C. Rillig, J. Thies, C. A. Masiello, W. C. Hockaday, D. Crowley,

Biochar effects on soil biota – A review, Soil Biol. Biochem. 43 (2011) 1812-1836.

[33] J. Gaunt, J. Lehmann, Energy balance and emissions associated with biochar

sequestration and pyrolysis bioenergy production, Environ. Sci. Tech. 42 (2008) 4152-

4158.

[34] D. Woolf, J. E. Amonette, F. A. S. Perrott, J. Lehmann, S. Joseph, Sustainable

biochar to mitigate global climate change, Nature Comm. 1 (2010) 1-9.

[35] T. M. Suguihiro, P. R. Oliveira, E. I. P. Rezende, A. S. Mangrich, L. H.

Marcolino-Junior, M. F. Bergamini, An electroanalytical approach for evaluation of

biochar adsorption characteristics and its application for Lead and Cadmium

determination, Bioresour. Technol. 143 (2013) 40-45.

[36] P. R. Oliveira, A. C. Lamy-Mendes, E. I. P. Rezende, A. S. Mangrich, L. H.

Marcolino-Junior, M. F. Bergamini, Electrochemical determination of copper ions in

spirit drinks using carbon paste electrode modified with biochar, Food Chem. 171

(2015) 426-431.

[37] Brazil. Ordinance No. 27 of March 18, 1996. Official Gazette of the Union, Brasilia

20 March 1996.

[38] H. Lu, W. Zhang, Y. Yang, X. Huang, S. Wang, R. Qiu, Relative distribution of Pb2+

sorption mechanisms by sludge-derived biochar, Water Research 46 (2012) 854-862.

17
[39] E. Shams, R. Torabi, Determination of nanomolar concentrations of cadmium by

anodic-stripping voltammetry at a carbon paste electrode modified with zirconium

phosphated amorphous silica, Sens. Actuat. B 117 (2006) 86-92.

[40] F. Aduini, J. Q. Calvo, A. Amine, G. Palleschi, D. Moscone, Bismuth-modified

electrodes for lead detection, Trends in Anal. Chem. 29 (2010) 1295-1304.

[41] V. N. Nurchi, I. Villaescusa, The Chemistry Behind the Use of Agricultural Biomass

as Sorbent for Toxic Metal Ions: pH Influence, Binding Groups, and Complexation

Equilibria, Intech 1 (2011) 409-424.

[42] Z. Bi, C. S. Chapman, P. Salaun, C. M. G. van den Berg, Determination of Lead

and Cadmium in Sea- and Freshwater by Anodic Stripping Voltammetry with a

Vibrating Bismuth Electrode, Electroanal. 22 (2010) 2897-2907.

[43] A. E. Martell, R. M. Smith, Critical Stability Constants. New York: Plenum, 1989.

[44] J. Saturno, D. Valera, H. Carrero, L. Fernández, Electroanalytical detection of Pb,

Cd and traces of Cr at micro/nano-structured bismuth film electrodes, Sensors and

Actuators B: Chemical 159 (2011) 92-96.

[45] W. Siriangkhawut, S. Pencharee, K. Grudpan, J. Jakmunee, Sequential injection

monosegmented flow voltammetric determination of cadmium and lead using a bismuth

film working electrode, Talanta 79 (2009) 1118-1124.

[46] A. A. A. Khan, M. A. Abdullah, Bismuth-modified Hydroxyapatite Carbon Electrode

for Simultaneous in-situ Cadmium and Lead Analysis, International Journal of

Electrochemical Science, 8 (2013) 195-203.

[47] Y. Wu, N. B. Li, H. Q. Luo, Simultaneous measurement of Pb, Cd and Zn using

differential pulse anodic stripping voltammetry at a bismuth/poly(p-aminobenzene

sulfonic acid) film electrode, Sensors and Actuators B: Chemical 133 (2008) 677-681.

[48] Q. M. Feng, Q. Zhang, C. G. Shi, J. J. Xu, N. Bao, H. Y. Gu, Using nanostructured

conductive carbon tape modified with bismuth as the disposable working electrode for

stripping analysis in paper-based analytical devices, Talanta, 115 (2013) 235-240.

18
[49] G. D. Pierini, A. M. Granero, M. S. D. Nezio, M. E. Centurión, M. A. Zon, H.

Fernández, Development of an electroanalytical method for the determination of lead in

Argentina raw propolis based on bismuth electrodes, Microchemical Journal 106 (2013)

102-106.

[50] G. H. Hwang, W. K. Han, J. S. Park, S. G. Kang, Determination of trace metals by

anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode,

Talanta, 76 (2008) 301-308.

[51] Brazil, Resolution No. 430 of May 13, 2011. Complements and amending the

Resolution No. 357/2005. Official Gazette of the Union, Brasilia 14 May 2011.

19
 LIST OF TABLES

Table 1

Table 1- Analytical performance for Pb(II) determination by DPV, SWV and LSV using

the proposed sensor.

DPV SWV LSV

-1
Linear range (nmol L ) 10 - 5000 50 - 1000 500 - 10000
-1
Sensitivity (µA L µ mol ) 29.61 151.64 3.80

Correlation coeficient 0.9997 0.9991 0.9995

-1
Limit of detection - LOD (nmol L ) 2.83 7.00 149
-1
Limit of quantification - LOQ (nmol L ) 9.43 23.3 495

20
 Table 2

Table 2- Comparison of present work and other bismuth modified electrodes for the

determination of Pb(II).

Electrode Technique LOD Linear range Ref.

-1 -1
(nmol L ) (nmol L )

µ-NP/BiFE DPAdSV 87 482.6 – 1930.5 [44]

BiFE SWASV 33 50–482.6 [45]

Bi-HA CME SWASV 24 50–965.3 [46]

Bi/poly(p-ABSA) film electrode DPASV 3.7 5 – 627.4 [47]

Bismuth modified carbon tape electrode SWASV 9.6 50 – 2413.1 [48]

BiFE SWASV 2.9 5 – 241.3 [49]

Bi-CNT electrode SWASV 6.3 9.6 – 482.6 [50]

nBi-BchDCPE DPAdSV 1.4 5 - 1000 This work

µ-NP/BiFE: micro/nanoparticle bismuth film electrode; DPAdSV: differential pulse adsorptive

stripping voltammetry; BiFE: bismuth film electrode; SWASV: square wave anodic stripping

voltammetry; Bi-HA CME: Bismuth-modified Hydroxyapatite Carbon Electrode; Bi/poly(p-ABSA)

film electrode: bismuth/poly(p-aminobenzene sulfonic acid) film electrode; Bi-CNT electrode:

bismuth-modified carbon nanotube electrode; nBi-BchDCPE: nano-bismuth modified biochar

doped carbon paste electrode.

21
 CAPTIONS OF FIGURES

Fig. 1 – DPAdSV of 1.0 x 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 + 0.1 mol L-1 KNO3. Reduction potential: -

0.8 V, reduction time: 30 s, potential scan: −0.8 to +0.5 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 µmol L-1 of Pb(II) ions for 5 min.

Fig. 2 - (A) SEM micrograph of nBi-BchCPE with magnification of 25 kx. (B) Detail of

bismuth nanosctructures in 132 kx. (C) Size distribution graph of bismuth

nanosctructures. (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 (n = 3) current

for bismuth and Lead oxidation. Pre-concentration step in 0.01 mol L-1 acetate buffer

pH 6 containing 10 µmol L-1 of Pb(II) ions for 5 min (n = 3).

Fig. 4 – DPV measurements under optimized conditions for Pb(II) using nBi-BchCPE.

(A) Pb(II) concentration ranging from 0 – 1.0 µmol L-1; Pb(II) concentration ranging from

0 – 0.1 µmol L-1; (C) Calibration plot (n = 3).

Fig. 5 – Correlation plot for analysed samples using results obtained by proposed

sensor and those provided by ICP-OES methodology.

22
 RESEARCH HIGHLIGHTS

- Electrochemical procedure for growth of bismuth nanostructures

anchored by biochar;

- Low cost and easy preparation of voltammetric sensor for Pb(II)

determination;

- Excellent analytical performance: low limit of detection, high

sensitivity and stability of the proposed sensor;

- Good agreement with ICP-OES methodology for determination of

Pb(II) released from ceramic dishes.

23
Figure 1
Figure 2A
Figure 2B
Figure 2C
Figure 2D
Figure 3
Figure 4

Figure 4

100
A B 80 C
12
75
60
10
50 40

I / mA

I / mA
Iap / mA

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 -1
2+
E / V vs. Ag/AgCl KCl 3 mol L CPb / mmol L
Figure 5
 0.1 mol L-1
b

a
Acetic Acid c

Pb(II) released solutions

Ceramic Dishes

200
Pb° → Pb2+ + 2e-
150

100

I / mA
50

0
-0.8 -0.6 -0.4
E / V vs. Ag/AgCl
Pb(II) determination nBi + Biochar Electrode