Tal D 15 00833R3

Elsevier Editorial System(tm) for Talanta
Manuscript Draft
Manuscript Number: TAL-D-15-00833R3
Title: Sensitive voltammetric determination of Lead released from ceramic dishes by using of bismuth
nanostructures anchored on biochar
Article Type: Research Paper
Keywords: Bismuth nanostructures; Electrochemical Sensor; Lead; Ceramic dishes
Corresponding Author: Prof. Luiz Humberto Marcolino-Junior,
Corresponding Author's Institution:
First Author: Deonir Agustini
Order of Authors: Deonir Agustini; Antonio S Mangrich; Marcio F Bergamini; Luiz Humberto
Marcolino-Junior
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 Lead (II) ions followed by reduction 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.
Cover Letter
U N I V E R S I D AD E F E D E R AL D O P AR AN Á
Centro Politécnico
D E P AR T AM E N T O D E Q U Í M I C A
P.O. Box 19032, CEP 81531-980, Curitiba - PR, Brazil.
e-mail: luiz1berto@ufpr.br
March, 15th, 2015.
Dear Editor,
I would like to submit for appreciation of Talanta the manuscript: “Sensitive voltammetric
determination of Lead released from ceramic dishes by using of bismuth nanostructures
anchored on biochar”. The cited manuscript describes for the first time the use of biochar as
support for preparation of bismuth nanostructures and its application for voltammetric
determination of Lead ions released from ceramic dishes.
Thank you very much for your attention.

Sincerely yours,
Dr. Luiz Humberto Marcolino-Junior

Laboratory of Electrochemical Sensors (LabSensE)
Response to Reviewers
Centro Politécnico
P.O. Box 19032,CEP 81531-980, Curitiba - PR, Brazil.
April 16th, 2015.
Prof. Dr. Jose Luis Burguera

Editor of Talanta
Correspondence reference: TAL-D-15-00833R2
“Sensitive voltammetric determination of Lead released from ceramic dishes by using of bismuth
nanostructures anchored on biochar”
Dear Editor,
Please, as previously suggested, we are sending a rewritten/revised copy of the above cited
manuscript. I would like to acknowledge for the insightful suggestions and comments. The answers
and comments about the points picked up are listed below and all changes made in the manuscript
were highlighted in the revised version. We now believe that the manuscript is appropriate, but if
you think that any changes are needed please contact us.
Editor’s comments
The English still requires of a revision. There are several spelling mistakes and careless errors,
which authors could have corrected before re-submission. As well, there are some grammatical
errors as well as punctuation marks especially commas, spacing between some words, and dots are
not used in many cases. In all the cases, please insert commas wherever necessary. See e.g.:
..traces of Lead ... should be: ...traces of lead ...
..reported by Suguihiro et al .... Should be: ....reported by Suguihiro et al. ....
..Oliveira et al .....it should be: ....Oliveira et al. ...
..Under these conditions Pb(II) ions.. it should be: ...Under these conditions, Pb(II) ions....
..Proposed sensor has shown ....it should be: ....The proposed sensor has shown ....
Acetate buffer solutions (0.01 mol L-1) and not: Acetate buffer solutions (0.01mol L-1) .
.Series equipment was used.... and not: ...Series equipmentwas used....
All changes were provided (and highlighted) in the manuscript. The use of
commas and dots was revised in a whole…
The word Figure must be shortened to Fig., except when starting a new phrase (only in the last case
must be written the whole word).
Done.
Thank you in advance for your kind attention,
Best Regards,
Dr. Luiz Humberto Marcolino-Junior

Laboratório de Sensores Eletroquímicos (LabSensE)
Novelty Statement
Centro Politécnico
P.O. Box 19032, CEP 81531-980, Curitiba - PR, Brazil.
March, 15th, 2015.
NOVELTY STATEMENT
 Biochar is a carbonaceous materials poorly explored for electrode modification. So, there is
a novelty in its use for Chemically Modified Electrode (CME) preparation;
 Narrow distribution of bismuth nanostructures size obtained by exploring of biochar
adsorption properties and improvement on the voltammetric stripping signal provided by
elevated Lead concentration into bismuth nanostructures;
 The method offers an analytical performance (Limit of Detection, Linear Dynamic Range
and Selectivity) adequate when compared with others Electroanalytical methodologies;
 Good analytical performance for determination of Pb(II) released from ceramic dishes in
comparison with ICP-OES methodology.

*Highlights (for review)
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.

*Graphical Abstract (for review)
0.1 mol L-1

b
a
Acetic Acid c
Pb(II) released solutions

Ceramic Dishes
200
Pb° → Pb2+ + 2e-
150
I / A
100
50
0
-0.8 -0.6 -0.4
E / V vs. Ag/AgCl
Pb(II) determination nBi + Biochar Electrode
*Revised Manuscript (With Track Changes)
Sensitive voltammetric determination of lead released from ceramic

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2 dishes by using of bismuth nanostructures anchored on biochar
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7 Deonir Agustinia, Antonio Salvio Mangrichb,c, Márcio F. Bergaminia, Luiz Humberto
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9 Marcolino-Juniora*
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16 a- Laboratório de Sensores Eletroquímicos (LabSensE), Departamento de Química,
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18 Universidade Federal do Paraná (UFPR), CEP 81.531-980, Curitiba-PR, Brazil.
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25 b- Laboratório de Química de Húmus e Fertilizantes, Departamento de Química,
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34 c- Instituto Nacional de Ciência e Tecnologia de Energia e Ambiente (INCT
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36 E&A/CNPq), Brazil.
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47 *email address: luiz1berto@ufpr.br
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49 Telephone number: +55 41 3361-3177
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52 Fax number: +55 41 3361-3186
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Abstract
1
2 A simple and sensitive electroanalytical method was developed for determination of
3
4 nanomolar levels of Pb(II) based on the voltammetric stripping response at a carbon
5
6
7
paste electrode modified with biochar (a special charcoal) and bismuth nanostructures
8
9 (nBi-BchCPE). The proposed methodology was based on spontaneous interactions
10
11 between the highly functionalized biochar surface and Pb(II) ions followed by reduction
12
13 of these ions into bismuth nanodots which promote an improvement on the stripping
14
15
anodic current. The experimental procedure could be summarized in three steps,
16
17
18 including an open circuit pre-concentration, reduction of accumulated lead ions at the
19
20 electrode surface and stripping step under differential pulse voltammetric conditions
21
22 (DPAdSV). SEM images revealed dimensions of bismuth nanodots ranging from 20 nm
23
24 to 70 nm. The effects of main parameters related to biochar, bismuth and operational
25
26
27 parameters were examined in detail. Under the optimal conditions, the proposed
28
29 sensor has exhibited linear range from 5.0 to 1,000 nmol L-1 and detection limit of 1.41
30
31 nmol L-1 for Pb(II). The optimized method was successfully applied for determination of
32
33 Pb(II) released from overglaze-decorated ceramic dishes. Results obtained were
34
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36
compared with those given by inductively coupled plasma optical emission
37
38 spectroscopy (ICP-OES) and they are in agreement at a 99% of confidence level.
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40
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42 Keywords: Bismuth nanostructures; Electrochemical Sensor; Lead; Ceramic dishes.
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1. Introduction
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2 Lead is one of the most useful metals used since ancient civilizations because
3
4 of its abundance, low cost and ease in their applications [1]. However, it is
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characterized by serious effects on human health being absorbed and accumulated in
8
9 the body, affecting heart, bones, intestines, kidneys, reproductive and nervous systems
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11 [2], lag in learning and low neurological development in children [3]. Although several
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13 efforts have been made to reduce the exposure to this metal, a large number of people
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continue being polluted by lead due to many sources of exposure like paints, water,
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18 food, dust, soil, kitchen utensils and leaded gasoline [4]. For these reasons, the
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20 determination of traces of lead in different matrices has a great importance. The
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22 certified standard techniques include electrothermal atomic absorption spectrometry
23
24 (ET-AAS), flame atomic absorption spectrometry (FAAS), inductively coupled plasma
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26
27 mass spectrometry (ICP-MS) and inductively coupled plasma optical emission
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29 spectrometry (ICP-OES) [5-7]. Although these techniques are very sensitive, they have
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31 the disadvantages such as high cost, complicated and inadequate instrumentation for
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33 field application.
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An interesting alternative method for determination of Pb(II) and other species
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38 at trace and ultra-trace levels is stripping voltammetry, specially those invoving
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40 adsorptive steps [8-10]. This is one of the most accessible and widely used techniques
41
42 [11] characterized by a remarkable sensitivity, low cost, simple equipment, rapid
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44
analysis and the possibility of analyses in colored samples or with dispersed solid
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47 particles [12]. Regarding electrode materials, mercury has been widely used in
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49 stripping analysis of lead due its ability of yield amalgam with the analyte, wide
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51 potential window, high sensitivity and reproducibility [13, 14]. High toxicity, difficulties
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53 with storage and disposal of mercury has stimulated the research for other materials
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56 with similar electroanalytical characteristics and low toxicity [15-17].
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58 Bismuth modified electrodes provided an alternative material for
59
60 electrochemical stripping analysis. This metal was introduced by Wang with coworkers
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62 1
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in 2000 [18] and it has excellent chemical and electrochemical characteristics such as
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2 low toxicity, ability to form alloys with different metals, wide potential ranges and low
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4 sensitivity to dissolved oxygen [19]. Bismuth modified electrodes are usually built on
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different substrates: gold, platinum, glassy carbon, screen-printed ink, carbon fiber or
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9 carbon pastes [20]. The latter has been widely used due its inexpensive and easy
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11 preparation, renewable surface and stability in different solvents [21].
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13 The most common procedures used for preparing bismuth-film modified
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electrodes are the in situ [22] or ex situ [23, 24]. Some other procedures including
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18 carbon paste containing bismuth precursor or powder such as the incorporation of
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20 Bi2O3 with subsequent reduction to metallic bismuth [25]. In the last years, the
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22 electrode modification with bismuth nanostructures have been proposed to combine
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24 the electrochemical bismuth characteristics with the inherent advantages of
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27 nanomaterials such as enhanced mass transport, high surface area and improved
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29 signal-to-noise ratio [26,27]. However, the fabrication of nano-bismuth is characterized
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31 for complicated synthesis, complex instrumentation or long time reduction [28-30]. An
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33 alternative route for simple and rapid construction of bismuth nanostructures at an
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electrode surface could be achivied by using of functionalized materials to support the
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38 bismuth ions before the electrochemical reduction.
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40 Biochar is a kind of carbonaceous material easily obtained by thermal
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42 degradation (pyrolysis) of biomass (such as crop residues, wood scraps, municipal and
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industrial solid waste and animal manure) in the absence of air [31]. The production of
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47 biochar can be considered as low-cost and environmental friendly and its applications
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49 include soil amendment, power source conversion processes, carbon sequestration
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51 and as sorbent material for the removal of organic and inorganic contaminants in soil
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53 and water [32-34]. In these works, biochar has exhibited high removal capacity,
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56 especially for metallic ions, in a relatively short time when compared with other sorbent
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58 materials. This adsorption capacity of biochar was exploited in electrochemical
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60 stripping measurements only in two works previously reported by Suguihiro et al. [35]
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for Pb(II) and Cd(II) determination in water samples and Oliveira et al. [36] for Cu (II)
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2 determination on spirit drinks. Its use as platform for growth of metallic nanostructures
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4 has not been explored yet.
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In this paper, we report for the first time the development of easy and sensitive
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9 nBi-BchCPE for in-field pre-concentration and fast quantification of Pb(II) by differential
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11 pulse adsorptive stripping voltammetry (DPAdSV). The main novelty of this work is the
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13 use of biochar simultaneously as platform for growth of Bi nanostructures as well as
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spontaneous pre-concentration and subsequent determination of Pb(II) ions. Under
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18 these conditions, Pb(II) ions can be pre-concentrated simultaneously using different
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20 electrodes (as passive samplers) which make possible rapid and consecutive
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22 measurements. The proposed sensor has shown a synergic effect based on the high
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24 adsorption capacity of biochar for Bi(III) and Pb(II) ions and the enhancement of the
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27 electrochemical response characterized by presence of Bi nanostructures on the
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29 electrode surface. The proposed electrode was applied for trace determination of
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31 Pb(II) released from overglaze-decorated ceramic dishes samples and the results were
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33 compared with ICP-OES.
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38 2. Experimental
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40 2.1. Material and reagents
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42 The biochar (with a particle size of 80 meshes) was produced from castor oil
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cake by pyrolysis at 300°C with a heating rate of 10°C per minute (60 minutes of
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47 residence time). All chemicals had analytical reagent grade and used without further
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49 purification. The solutions were prepared with purified water in a Millipore Milli-Q
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51 system. A standard solution containing 1000 mg L-1 Pb(II) (Merck) was used as stock.
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53 Solutions containing different concentrations of Pb(II) ions were made by dilution in
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56 water. Bi(III) ion solution (3.0 mmol L-1) was prepared by dissolving Bi(NO3)3·5H2O in
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58 0.04 mol L-1 HNO3. Acetate buffer solutions (0.01 mol L-1) were made by mixing
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60 appropriated volumes of 0.05 mol L-1 sodium acetate solution with 0.05 mol L-1 acetic
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acid solution; the required pH was adjusted with a sodium hydroxide solution.
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2 Potassium nitrate solution (0.1 mol L-1) was prepared by dilution of KNO3 in purified
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4 water.
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9 2.2. Apparatus
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11 Voltammetric measurements were performed in a µAUTOLAB Type III
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13 (Metrohm) connected to a microcomputer controlled by software (NOVA 1.7) for data
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acquisition and instrumental control. All electrochemical experiments were carried out
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18 in a three-electrode configuration employing a nBi-BchCPE as the working electrode,
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20 platinum wire as counter electrode and Ag/AgCl (3.0 mol L-1 KCl) as reference
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22 electrode. All the experiments were performed in a 25 mL glass cell at room
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24 temperature and without removing oxygen.
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27 A Metrohm 780 pH meter was used to determine the pH of solutions. Scanning
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29 Electron Microscopy (SEM) images were obtained from a Quanta 450 ESEM FEG and
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31 Energy Dispersive X-ray Spectroscopy (EDS) analysis were performed from an EDAX
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33 microanalysis. For the ICP-OES Pb(II) measurements a Thermo Scientific, model 6000
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Series equipment was used.
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40 2.3. Preparation of the modified carbon paste electrode
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42 The carbon paste electrode modified with biochar (BchCPE) was prepared by
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carefully mixing the dispersed graphite powder (45–75% (w/w)) (Fischer), with biochar
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47 (0–30% (w/w)) and mineral oil (25% (w/w)). The components were mixed manually in a
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49 mortar and pestle for at least 10 min to obtain an appropriate homogenization.
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51 Subsequently, the modified carbon paste was packed into piston-driven electrode
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53 holder (PVC cylindrical tube, i.d. 3.0 mm) and arranged with a copper wire serving as
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56 an external electric contact. The electrode surface was smoothed by polishing on a
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58 piece of paper. For the carbon paste electrode modified with biochar and bismuth
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60 nanostructures (nBi-BchCPE) preparation, the carbon paste electrode modified only
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with biochar (BchCPE) was placed in 10 mL of Bi(III) ions solution for 30 s under no
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2 applied potential and stirring conditions.
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2.4. Measurement procedure
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9 The voltammetric measurements were performed by adsorptive stripping
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11 voltammetry. For pre-concentration step, the nBi-BchCPE was immersed in a stirred 10
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13 mL of 0.01 mol L-1 acetate buffer solution (pH 6) containing Pb(II) for 5 minutes at open
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circuit potential. The electrode was then removed from the pre-concentration cell,
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18 gently rinsed with 0.01 mol L-1 acetate buffer, placed in the electrochemical cell
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20 containing 10 mL of a quiescent supporting electrolyte (0.01 mol L-1 acetate buffer pH
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22 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-
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24 1
) for 30 s. After that, the voltammograms were recorded by applying a potential scan
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27 from −0.8 to +0.5 V under differential pulse voltammetry conditions with potential
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29 amplitude of 100 mV, pulse time of 25 ms and step potential of 5 mV. Finally, the
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31 electrode surface was renewed by mechanical polishing in paper.
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2.5. Analysis of real samples
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38 The leaching of Pb(II) present in these dishes was performed according to
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40 methodology adapted from ANVISA [37]. For the release test, it was used 0.1 mol L-1
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42 acetic acid solution for 2 hours at a temperature of 80°C. An aliquot of the resulting
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solution was added to the pre-concentration solution so that the concentration of Pb(II)
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47 stays within the linear range of techniques. Six brands of Chinese (porcelain / ceramic)
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49 dishes were evaluated with the techniques of DPAdSV (using the nBi-BchCPE) and
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51 ICP-OES.
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56 3. Results and discussion
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58 3.1. Voltammetric performance of Bi-BchCPE for Pb(II) determination
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The addition of the modifiers (biochar and bismuth) in the carbon paste aims to
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2 improve the adsorption and, consequently, the detectability of Pb(II). To evaluate the
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4 effect of the modifiers in the voltammetric response, the CPE, BchCPE and Bi-BchCPE
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were submitted to measurements after pre-concentration step in solution containing a
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9 10 µmol L-1 of Pb(II) ions. In Fig. 1A, the CPE presented a very low adsorption capacity
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11 and negligible response. However, the signal observed for lead oxidation (Epa = - 0.57
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13 V) using the BchCPE (Fig.1B) is remarkably higher than CPE which can be attributed
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to the presence of biochar in the paste due to phenomena such as metal exchange,
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18 complexation with functional groups, surface precipitation or physical adsorption that
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20 can significantly increases the pre-concentration of Pb(II) on the electrode surface [38].
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22 Finally the Fig. 1C represents the peak current of Pb(II) in Bi-BchCPE being
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24 remarkably greater than BchCPE, which clearly confirms the efficiency in the use of
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27 proposed sensor to the determination of Pb(II) due to the inherent advantages of the
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29 bismuth. Bismuth oxidation can be observed at potential of -0.10 V.
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31 Fig. 1
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3.2. SEM and EDS characterization of modified carbon paste electrodes
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38 The size and distribution of bismuth anchored on the BchCPE can affect
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40 significantly the determination of Pb(II). Fig. 2A shows a homogeneous dispersion of
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42 bismuth nanostructures (light gray spherical nanodots with some white agglomerates)
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on the biochar particles incorporated on the electrode surface which can be observed
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47 in detail in Fig. 2B. Fig. 2C shows the size distribution graph obtained by manual
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49 counting of at least 500 structures, which indicates an average size of 42±3 nm. The
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51 obtained bismuth nanostructures were manufactured and deposited on the electrode
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53 surface by using an easier strategy in comparison with some other reported [22].
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56 To investigate the interaction between biochar, bismuth and lead, EDS
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58 measurements were performed in BchCPE and nBi-BchCPE before and after pre-
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60 concentration in solution containing 10 µmol L-1 of Pb(II) ions. For individual
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determination of lead and bismuth was necessary to investigate the less intense peaks
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2 of the layers Lα and Lβ for these metals in order to avoid signal overlap. A good
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4 separation of these layers were obtained, with values of 10.51; 10.80; 12.56 and 12.97
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keV to Pb Lα, Bi Lα, PbLβ and Bi Lβ respectively. As can be seen in Fig. 2D, the
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9 BchCPE (Fig 2D-Curve I) before pre-concentration of lead, the EDS spectrum has not
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11 indicated the presence of any element which could interfere with the identification of
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13 bismuth or lead. After pre-concentration of Pb(II) in BchCPE (Fig 2D-Curve II), it was
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possible to observe the characteristic peaks of Pb Lα (10.51 keV) and Pb Lβ (12.56
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18 keV). For nBi-BchCPE (Fig 2D-Curve III), before the pre-concentration of lead, it was
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20 noted peaks of Bi Lα (10.80 keV) and Bi Lβ (12.97 keV) confirming the incorporation of
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22 bismuth in the biochar. Finally, for nBi-BchCPE after pre-concentration and reduction of
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24 Pb(II) (Fig 2D-Curve IV) the EDS spectrum taken from a nanodot has revealed the
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27 presence of both Bi and Pb in the same nanostructure. These results confirm not only
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29 the pre-concentration of analyte at the electrode surface but also they suggest strongly
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31 the formation of alloy between lead with bismuth.
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33 Fig. 2
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38 3.3. Influence of experimental parameters on the voltammetric response nBi-BchCPE
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40 In order to obtain the best voltammetric behavior of the nBi-BchCPE for Pb(II)
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42 determination, several parameters related to paste compositon, bismuth incorporation,
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pre-concentration solution and operational parameters were examined in detail.
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47 The amount of biochar added in the nBi-BchCPE has a significative influence
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49 on the voltammetric responses. Electrodes with different percentages of biochar were
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51 prepared and examined for their voltammetric signals to Pb(II) under identical
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53 conditions. The peak currents for Pb(II) have increased with increasing the amount of
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56 biochar in the nBi-BchCPE due to the increased adsorption capacity of the electrode.
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58 At 25% (w/w) of biochar the highest peak current was obtained. For amounts of biochar
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60 higher than 25% the response of the nBi-BchCPE decreased due the reduction in
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conductivity of the modified electrode [39]. According to these results a carbon paste
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2 composition of 25% biochar, 50% graphite and 25% mineral oil was used in further
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4 studies.
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The presence of bismuth nanostructures on the electrode surface is
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9 fundamental to its high sensitivity to the determination of Pb(II). For a fast and stable
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11 incorporation of nano-bismuth the pH of the solution has great influence. In this way,
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13 pH solutions ranging from 0.5 to 2.0 were used to study the grafting of Bi(III) ions on
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the electrode surface. The maximum incorporation was achieved at pH 1.5, whereas at
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18 low pH values a strong competion occurred between Bi(III) and H+ ions for adsorption
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20 sites of biochar. At pH above 1.5, there is a spontaneous process of hydrolysis of
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22 bismuth ions according to the reaction [40] Bi3+ + 3H2O  Bi(OH)3 + 3H+, limiting the
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24 use of adsorption solutions of Bi(III) at pH values around 1.5.
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27 The effect of the amount of bismuth added on the biochar was evaluated by
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29 immersion of the electrode in the solution containing bismuth ions for different intervals
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31 of time ranging from 15 to 300 s. After that, the electrode was submitted to pre-
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33 concentration step in solution containing of 10 µmol L-1 Pb(II). As shown in Fig. 3, the
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faradaic signals observed for oxidation of bismuth have increased with increase of time
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38 suggesting an increase in the amount Bi(III) ions incorporated on the electrode surface.
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40 By other side, the stripping peak height of Pb(II) (Fig. 3) increased with increasing time
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42 of Bi(III) grafting from 15 to 30 s and it gradually decreases for values above 30 s
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probably by formation of large clusters of nano-bismuth with consequent saturation of
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47 adsorption sites of biochar. Therefore, the optimum time for Bi(III) incorporation was 30
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49 s, which was chosen for following further experiments.
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51 Fig. 3
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53 The adsorption of Pb(II) on the surface of nBi-BchCPE occurs in the pre-
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56 concentration solution and for efficient adsorption lead ions must be in their ionic free
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58 form. So, the effect of pH for pre-concentration of Pb(II) at the electrode surface was
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60 investigated in the range of 3.0 to 8.0. It was found that the peak current of Pb(II)
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increased with increasing the pH reaching a maximum at pH value of 6.0 and
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2 progressively decreased at higher pH values. At low pH values occurs the competition
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4 between Pb(II) and H+ ions for the adsorption sites on the electrode. For high pH
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values, the low response can be ascribed to the hydrolysis of lead [41, 42]. Therefore,
8
9 the following experiments were carried out in pre-concentration solution with pH 6.0.
10
11 To evaluate the dependence between peak current and pre-concentration time,
12
13 Pb(II) ions were accumulated on the nBi-BchCPE using pre-concentration time varying
14
15
from 1 to 30 minutes. Anodic peak currents for Pb(II) have increased as the time pre-
16
17
18 concentration increases indicating a progressive increase in the amount of Pb(II)
19
20 adsorbed on the electrode. The peak currents start to stabilize after 15 minutes of pre-
21
22 concentration due to the equilibrium between ions in solution and those adsorbed on
23
24 the electrode surface. For further studies, an accumulation time of 5 minutes was used
25
26
27 in order to find a better combination between sensitivity and time of analysis.
28
29 In order to evaluate the effect of the composition of supporting electrolyte in the
30
31 voltammetric signal of Pb(II), phosphate buffer and acetate buffer solutions (both at pH
32
33 4.5) were studied. The best response was reached with measurements using acetate
34
35
36
buffer solutions due to the low tendency of formation of stable acetate-complexes with
37
38 Pb(II) being indicated by the stability constants for [Pb(Ac)]+ and [Pb(Ac)2], which are
39
40 reported as logK=2,68 and logK=4,08, respectively. These constants are significatively
41
42 lower than phosphate-Pb(II) species [PbHPO4] and [PbH2PO4]+, which have stability
43
44
constants of logK=15.48 and logK=21.07, respectively [40]. The influence of acetate
45
46
47 buffer concentration was studied in the range of 0.01 to 0.5 mol L-1 at pH 4.5 (controlled
48
49 ionic strength). Maximum peak current was obtained at 0.01 mol L-1 and a progressive
50
51 decrease for higher concentrations of acetate buffer solution was observed. Thus, a
52
53 supporting electrolyte consisting of 0.01 mol L-1 acetate buffer and 0.1 mol L-1 of KNO3
54
55
56 was selected for further studies.
57
58 The effect of pH of supporting electrolyte on the voltammetric responses of
59
60 Pb(II) was also studied for pH values between 2.0 and 7.0. Maximum peak current was
61
62 9
63
64
65
obtained at pH 4.5. At lower pH values the reduction in the magnitudes of voltammetric
1
2 signal can be attributed to replacement of Pb(II) pre-concentrated on the electrode
3
4 surface by H+ ions. For these reasons, the optimum pH of 4.5 was selected for
5
6
7
following experiments.
8
9 Beyond the general characteristics of the system above mentioned,
10
11 instrumental parameters can affect significantly the electrode response.The effect of
12
13 the reduction potential was studied in the range of −1.3 V to −0.6 V to the stripping
14
15
peak heights of Pb(II). The best result was obtained at -0.8 V since in more positive
16
17
18 potential values the reduction of Pb(II) become incomplete due to the proximity of the
19
20 redox potential of lead. For potential values more negative than -0.8 V there was a
21
22 gradual and slight interference of H+ ions in the reduction of lead. Reduction time
23
24 applied before voltammetric scan was investigated in the range of 0–120 s and it has
25
26
27 demonstrated a gradual increase in the response between 0 and 30 seconds, followed
28
29 by stabilization of current values over this time indicating that 30 s are enough for the
30
31 effective reduction of Pb(II) ions previously adsorbed. Based on these results, a
32
33 reduction potential of −0.8 V for 30 s was selected for further optimization studies.
34
35
36
37
38 3.4. Analytical performance of nBi-BchCPE
39
40 In order to obtain the best analytical performance for the proposed sensor,
41
42 calibration curves for Pb(II) were obtained by using of DPV, SWV and LSV under
43
44
optimal conditions (not shown). Table 1 shows the figures of merit of nBi-BchCPE for
45
46
47 each voltammetric technique used; the limit of detection (LOD) was estimated based
48
49 on three times the blank standard deviation divided by slope of the calibration curve
50
51 and the limit of quantification (LOQ) was calculated based on ten times the blank
52
53 standard deviation divided by slope of the calibration curve.
54
55
56 Table 1
57
58 Calibration curves obtained using DPV have shown a linear response for a
59
60 wider concentration range of Pb(II) ions in comparison with other voltammetric
61
62 10
63
64
65
techniques evaluated. From Table 1, it was observed that LSV had the poorer
1
2 analytical performance probably due to the high capacitive current present in their
3
4 measurements, which resulted in a low sensitivity and high LOD and LOQ. The SWV
5
6
7
showed the best sensitivity (151.64 µA L µmol-1) and an elevated noise in the
8
9 background current. For these reasons, considering the best LOD and LOQ, DPV
10
11 (under optimized conditions: step potential of 5 mV, pulse time of 25 ms and potential
12
13 amplitude of 100 mV) was selected for analytical applications.
14
15
In order to improve the analytical performance of the proposed sensor
16
17
18 calibration curves were constructed using pre-concentration time of 20 minutes under
19
20 DPV conditions (Fig. 4A and 4B). Fig. 4C shows a calibration plot that was linear over
21
22 the range concentration from 5.0 to 1,000 nmol L-1 for Pb(II). The linear regression
23
24 equation found was I (μA) = -1.27 + 82,02CPb(II) (where CPb(II) in µmol L-1). The LOD
25
26
27 obtained was 1.41 nmol L-1 and the LOQ was 4.70 nmol L-1.
28
29 Fig. 4
30
31 In comparison with a previously described Pb(II) sensor with biochar in the
32
33 absence of bismuth [35] the proposed sensor reaches a limit of detection (LOD) almost
34
35
36
10-fold better. The analytical features of the proposed electrode were compared (Table
37
38 2) with other bismuth modified electrodes previously reported in the literature for Pb(II)
39
40 determination. Moreover, the main advantage of the proposed sensor is the Pb(II) pre-
41
42 concentration performed at open circuit potential conditions that allows its use as a
43
44
passive sampler (especially for environmental applications) as well as the possibility of
45
46
47 rapid consecutive measurements after pre-concentration step.
48
49 Table 2
50
51 The intra-day reproducibility study of the nBi-BchCPE was carried out based on
52
53 the DPV response to 10 µmol L-1 Pb(II) pre-concentrated for 5 minutes using 5 different
54
55
56 electrode surfaces. The relative standard deviation (RSD) found was 3.40%,
57
58 demonstrating good reproducibility of the nBi-BchCPE, which can be attributed to a
59
60 good control of the carbon paste preparation and modification with biochar and
61
62 11
63
64
65
bismuth. For inter-day reproducibility study the same experiment was repeated by five
1
2 consecutive days indicating a RSD < 5.0%.
3
4
5
6
7
3.5. Effect of concomitants species
8
9 The influence of ionic species on the voltammetric responses was examined
10
11 using solution containing Pb(II) ions (concentration fixed at 2.40 µmol L-1) and foreign
12
13 ionic species at concentration levels based on limit established by CONAMA (Brazilian
14
15
legislation) [51].The evaluated species were considered as interfering agent when the
16
17
18 electrochemical signal for Pb(II) exhibited a deviation more than ±5.0%. It was
19
20 observed that the presence of species Ag+, As3+, Ba2+, Cd2+, Cl-, Cr3+, Cr6+, F-, Hg2+,
21
22 Mn2+, Ni2+, NO3-, Se4+, SO42- and Zn2+ had no interference in the voltammetric response
23
24 of Pb(II) even at high concentration level. A significant decrease in peak currents for
25
26
27 Pb(II) was observed when Cu2+ (10-fold), Fe3+(100-fold) and Sn2+(15-fold) were present
28
29 in the pre-concentration solution indicating that these metal ions compete with Pb(II) for
30
31 the binding sites of biochar. However, interference effect observed is constant and it
32
33 could be minimized by using of standard addition procedure.
34
35
36
37
38 3.6. Analyses in real samples
39
40 The nBi-BchCPE was applied to the analysis of Pb(II) released from overglaze-
41
42 decorated ceramic dishes. The solution used in the release test (0.1 mol L-1 acetic acid)
43
44
was added directly to the pre-concentration solution without any sample pre-treatment.
45
46
47 Concentrations of lead ions were determined by standard addition method and the
48
49 voltammetric results obtained were validated using ICP-OES. Fig. 5 presents the
50
51 Pb(II) concentrations measured by the proposed electrode and the corresponding
52
53 ICP-OES results. A good agreement was found between the values obtained by
54
55
56 nBi-BchCPE and ICP-OES, with deviations less than 5.0 %. Linear regression obtained
57
58 from the Fig.5 has given a value of R = 0.99941, a slope of 0.99475 and an intercept
59
60 with a value of 0.12561. In addition, the paired t-test (99% confidence level and 5
61
62 12
63
64
65
degrees of freedom) indicates that there are no significant differences between the
1
2 results obtained by the two methods. Therefore, these results demonstrate that the
3
4 proposed electrode can be successfully applied in the determination of Pb(II) in real
5
6
7
samples.
8
9 Fig. 5
10
11
12
13 4. Conclusions
14
15
16
17
18 The incorporation of bismuth nanostructures on biochar allowed the
19
20 development of a new modified carbon paste electrode, which has exhibited detection
21
22 limits of nmol L-1 for Pb(II) due to the high adsorptive capacity of biochar coupled with
23
24 electrochemical advantages of bismuth in nanoscale. It was also observed that the
25
26
27 proposed electrode had a linear reponse for a wide range of Pb(II) concentration,
28
29 excellent reproducibility and few interfering ions. Thus, the main features of nBi-
30
31 BchCPE are low cost, ease of fabrication, able to portability (due to pre-concentration
32
33 step in open circuit), quickness and high sensitivity in the analyses. Finally, the
34
35
36
analyses of Pb(II) released from overglaze-decorated ceramic dishes without any
37
38 sample pre-treatment, proved the efficiency of the proposed electrode and showed its
39
40 potential for fast, easy and sensitive monitoring of Pb(II) in various samples.
41
42
43
44
Acknowledgements
45
46
47
48
49 We gratefully acknowledge financial support from Brazilian foundations:
50
51 Fundação Araucária, CAPES, and CNPq.
52
53
54
55
56
57
58
59
60
61
62 13
63
64
65
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1 LIST OF TABLES
2
3
4
5
6
7 Table 1
8
9
10
11
12
13 Table 1- Analytical performance for Pb(II) determination by DPV, SWV and LSV using
14
15 the proposed sensor.
16
17
18 DPV SWV LSV
19
20 -1
Linear range (nmol L ) 10 - 5000 50 - 1000 500 - 10000
21
22 -1
Sensitivity (µA L µ mol ) 29.61 151.64 3.80
23
24 Correlation coeficient 0.9997 0.9991 0.9995
25
26 -1
Limit of detection - LOD (nmol L ) 2.83 7.00 149
27
28 -1
29 Limit of quantification - LOQ (nmol L ) 9.43 23.3 495
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 20
63
64
65
1
2
3
4
5 Table 2
6
7
8
9
10
11 Table 2- Comparison of present work and other bismuth modified electrodes for the
12
13 determination of Pb(II).
14
15
16 Electrode Technique LOD Linear range Ref.
17 -1 -1
18 (nmol L ) (nmol L )
19
20 µ-NP/BiFE DPAdSV 87 482.6 – 1930.5 [44]
21
22 BiFE SWASV 33 50–482.6 [45]
23
24 Bi-HA CME SWASV 24 50–965.3 [46]
25
26
Bi/poly(p-ABSA) film electrode DPASV 3.7 5 – 627.4 [47]
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Bismuth modified carbon tape electrode SWASV 9.6 50 – 2413.1 [48]
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31 BiFE SWASV 2.9 5 – 241.3 [49]
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33 Bi-CNT electrode SWASV 6.3 9.6 – 482.6 [50]
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35 nBi-BchDCPE DPAdSV 1.4 5 - 1000 This work
36 µ-NP/BiFE: micro/nanoparticle bismuth film electrode; DPAdSV: differential pulse adsorptive
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38 stripping voltammetry; BiFE: bismuth film electrode; SWASV: square wave anodic stripping
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40 voltammetry; Bi-HA CME: Bismuth-modified Hydroxyapatite Carbon Electrode; Bi/poly(p-ABSA)
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42 film electrode: bismuth/poly(p-aminobenzene sulfonic acid) film electrode; Bi-CNT electrode:
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44
bismuth-modified carbon nanotube electrode; nBi-BchDCPE: nano-bismuth modified biochar
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doped carbon paste electrode.
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1
2 CAPTIONS OF FIGURES
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4
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6 Fig. 1 – DPAdSV of 1.0 x 10-5 mol L-1 Pb(II) at (A) CPE, (B) BchCPE and (C) Bi-
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8
9
BchCPE in 0.01 mol L-1 acetate buffer pH 4.5 + 0.1 mol L-1 KNO3. Reduction potential: -
10
11 0.8 V, reduction time: 30 s, potential scan: −0.8 to +0.5 V, potential amplitude: 100 mV,
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13 pulse time: 25 ms, step potential: 5 mV. Pre-concentration step in 0.01 mol L-1 acetate
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15 buffer pH 6 containing 10 µmol L-1 of Pb(II) ions for 5 min.
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Fig. 2 - (A) SEM micrograph of nBi-BchCPE with magnification of 25 kx. (B) Detail of
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23
24 bismuth nanosctructures in 132 kx. (C) Size distribution graph of bismuth
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26 nanosctructures. (D) EDX pattern of BchCPE and nBi-BchCPE before and after Pb(II)
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28 pre-concentration.
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34 Fig. 3 – Effect of time of incorporation of Bi(III) ions on the anodic peaks (n = 3) current
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37 for bismuth and Lead oxidation. Pre-concentration step in 0.01 mol L-1 acetate buffer
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39 pH 6 containing 10 µmol L-1 of Pb(II) ions for 5 min (n = 3).
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42
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44 Fig. 4 – DPV measurements under optimized conditions for Pb(II) using nBi-BchCPE.
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(A) Pb(II) concentration ranging from 0 – 1.0 µmol L-1; Pb(II) concentration ranging from
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49 0 – 0.1 µmol L-1; (C) Calibration plot (n = 3).
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55 Fig. 5 – Correlation plot for analysed samples using results obtained by proposed
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57 sensor and those provided by ICP-OES methodology.
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62 22
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*Revised Manuscript (clean copy)
Click here to view linked References
Sensitive voltammetric determination of lead released from ceramic

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2 dishes by using of bismuth nanostructures anchored on biochar
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7 Deonir Agustinia, Antonio Salvio Mangrichb,c, Márcio F. Bergaminia, Luiz Humberto
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9 Marcolino-Juniora*
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16 a- Laboratório de Sensores Eletroquímicos (LabSensE), Departamento de Química,
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25 b- Laboratório de Química de Húmus e Fertilizantes, Departamento de Química,
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34 c- Instituto Nacional de Ciência e Tecnologia de Energia e Ambiente (INCT
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36 E&A/CNPq), Brazil.
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47 *email address: luiz1berto@ufpr.br
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49 Telephone number: +55 41 3361-3177
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52 Fax number: +55 41 3361-3186
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Abstract
1
2 A simple and sensitive electroanalytical method was developed for determination of
3
4 nanomolar levels of Pb(II) based on the voltammetric stripping response at a carbon
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paste electrode modified with biochar (a special charcoal) and bismuth nanostructures
8
9 (nBi-BchCPE). The proposed methodology was based on spontaneous interactions
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11 between the highly functionalized biochar surface and Pb(II) ions followed by reduction
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13 of these ions into bismuth nanodots which promote an improvement on the stripping
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anodic current. The experimental procedure could be summarized in three steps,
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18 including an open circuit pre-concentration, reduction of accumulated lead ions at the
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20 electrode surface and stripping step under differential pulse voltammetric conditions
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22 (DPAdSV). SEM images revealed dimensions of bismuth nanodots ranging from 20 nm
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24 to 70 nm. The effects of main parameters related to biochar, bismuth and operational
25
26
27 parameters were examined in detail. Under the optimal conditions, the proposed
28
29 sensor has exhibited linear range from 5.0 to 1,000 nmol L-1 and detection limit of 1.41
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31 nmol L-1 for Pb(II). The optimized method was successfully applied for determination of
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33 Pb(II) released from overglaze-decorated ceramic dishes. Results obtained were
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compared with those given by inductively coupled plasma optical emission
37
38 spectroscopy (ICP-OES) and they are in agreement at a 99% of confidence level.
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40
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42 Keywords: Bismuth nanostructures; Electrochemical Sensor; Lead; Ceramic dishes.
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1. Introduction
1
2 Lead is one of the most useful metals used since ancient civilizations because
3
4 of its abundance, low cost and ease in their applications [1]. However, it is
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characterized by serious effects on human health being absorbed and accumulated in
8
9 the body, affecting heart, bones, intestines, kidneys, reproductive and nervous systems
10
11 [2], lag in learning and low neurological development in children [3]. Although several
12
13 efforts have been made to reduce the exposure to this metal, a large number of people
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continue being polluted by lead due to many sources of exposure like paints, water,
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18 food, dust, soil, kitchen utensils and leaded gasoline [4]. For these reasons, the
19
20 determination of traces of lead in different matrices has a great importance. The
21
22 certified standard techniques include electrothermal atomic absorption spectrometry
23
24 (ET-AAS), flame atomic absorption spectrometry (FAAS), inductively coupled plasma
25
26
27 mass spectrometry (ICP-MS) and inductively coupled plasma optical emission
28
29 spectrometry (ICP-OES) [5-7]. Although these techniques are very sensitive, they have
30
31 the disadvantages such as high cost, complicated and inadequate instrumentation for
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33 field application.
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36
An interesting alternative method for determination of Pb(II) and other species
37
38 at trace and ultra-trace levels is stripping voltammetry, specially those invoving
39
40 adsorptive steps [8-10]. This is one of the most accessible and widely used techniques
41
42 [11] characterized by a remarkable sensitivity, low cost, simple equipment, rapid
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44
analysis and the possibility of analyses in colored samples or with dispersed solid
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47 particles [12]. Regarding electrode materials, mercury has been widely used in
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49 stripping analysis of lead due its ability of yield amalgam with the analyte, wide
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51 potential window, high sensitivity and reproducibility [13, 14]. High toxicity, difficulties
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53 with storage and disposal of mercury has stimulated the research for other materials
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56 with similar electroanalytical characteristics and low toxicity [15-17].
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58 Bismuth modified electrodes provided an alternative material for
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60 electrochemical stripping analysis. This metal was introduced by Wang with coworkers
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62 1
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in 2000 [18] and it has excellent chemical and electrochemical characteristics such as
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2 low toxicity, ability to form alloys with different metals, wide potential ranges and low
3
4 sensitivity to dissolved oxygen [19]. Bismuth modified electrodes are usually built on
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different substrates: gold, platinum, glassy carbon, screen-printed ink, carbon fiber or
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9 carbon pastes [20]. The latter has been widely used due its inexpensive and easy
10
11 preparation, renewable surface and stability in different solvents [21].
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13 The most common procedures used for preparing bismuth-film modified
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15
electrodes are the in situ [22] or ex situ [23, 24]. Some other procedures including
16
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18 carbon paste containing bismuth precursor or powder such as the incorporation of
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20 Bi2O3 with subsequent reduction to metallic bismuth [25]. In the last years, the
21
22 electrode modification with bismuth nanostructures have been proposed to combine
23
24 the electrochemical bismuth characteristics with the inherent advantages of
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27 nanomaterials such as enhanced mass transport, high surface area and improved
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29 signal-to-noise ratio [26,27]. However, the fabrication of nano-bismuth is characterized
30
31 for complicated synthesis, complex instrumentation or long time reduction [28-30]. An
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33 alternative route for simple and rapid construction of bismuth nanostructures at an
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36
electrode surface could be achivied by using of functionalized materials to support the
37
38 bismuth ions before the electrochemical reduction.
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40 Biochar is a kind of carbonaceous material easily obtained by thermal
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42 degradation (pyrolysis) of biomass (such as crop residues, wood scraps, municipal and
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44
industrial solid waste and animal manure) in the absence of air [31]. The production of
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47 biochar can be considered as low-cost and environmental friendly and its applications
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49 include soil amendment, power source conversion processes, carbon sequestration
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51 and as sorbent material for the removal of organic and inorganic contaminants in soil
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53 and water [32-34]. In these works, biochar has exhibited high removal capacity,
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56 especially for metallic ions, in a relatively short time when compared with other sorbent
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58 materials. This adsorption capacity of biochar was exploited in electrochemical
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60 stripping measurements only in two works previously reported by Suguihiro et al. [35]
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62 2
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for Pb(II) and Cd(II) determination in water samples and Oliveira et al. [36] for Cu (II)
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2 determination on spirit drinks. Its use as platform for growth of metallic nanostructures
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4 has not been explored yet.
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In this paper, we report for the first time the development of easy and sensitive
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9 nBi-BchCPE for in-field pre-concentration and fast quantification of Pb(II) by differential
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11 pulse adsorptive stripping voltammetry (DPAdSV). The main novelty of this work is the
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13 use of biochar simultaneously as platform for growth of Bi nanostructures as well as
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15
spontaneous pre-concentration and subsequent determination of Pb(II) ions. Under
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18 these conditions, Pb(II) ions can be pre-concentrated simultaneously using different
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20 electrodes (as passive samplers) which make possible rapid and consecutive
21
22 measurements. The proposed sensor has shown a synergic effect based on the high
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24 adsorption capacity of biochar for Bi(III) and Pb(II) ions and the enhancement of the
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27 electrochemical response characterized by presence of Bi nanostructures on the
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29 electrode surface. The proposed electrode was applied for trace determination of
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31 Pb(II) released from overglaze-decorated ceramic dishes samples and the results were
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33 compared with ICP-OES.
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37
38 2. Experimental
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40 2.1. Material and reagents
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42 The biochar (with a particle size of 80 meshes) was produced from castor oil
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44
cake by pyrolysis at 300°C with a heating rate of 10°C per minute (60 minutes of
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46
47 residence time). All chemicals had analytical reagent grade and used without further
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49 purification. The solutions were prepared with purified water in a Millipore Milli-Q
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51 system. A standard solution containing 1000 mg L-1 Pb(II) (Merck) was used as stock.
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53 Solutions containing different concentrations of Pb(II) ions were made by dilution in
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56 water. Bi(III) ion solution (3.0 mmol L-1) was prepared by dissolving Bi(NO3)3·5H2O in
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58 0.04 mol L-1 HNO3. Acetate buffer solutions (0.01 mol L-1) were made by mixing
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60 appropriated volumes of 0.05 mol L-1 sodium acetate solution with 0.05 mol L-1 acetic
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62 3
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acid solution; the required pH was adjusted with a sodium hydroxide solution.
1
2 Potassium nitrate solution (0.1 mol L-1) was prepared by dilution of KNO3 in purified
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4 water.
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9 2.2. Apparatus
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11 Voltammetric measurements were performed in a µAUTOLAB Type III
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13 (Metrohm) connected to a microcomputer controlled by software (NOVA 1.7) for data
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acquisition and instrumental control. All electrochemical experiments were carried out
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18 in a three-electrode configuration employing a nBi-BchCPE as the working electrode,
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20 platinum wire as counter electrode and Ag/AgCl (3.0 mol L-1 KCl) as reference
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22 electrode. All the experiments were performed in a 25 mL glass cell at room
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24 temperature and without removing oxygen.
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27 A Metrohm 780 pH meter was used to determine the pH of solutions. Scanning
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29 Electron Microscopy (SEM) images were obtained from a Quanta 450 ESEM FEG and
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31 Energy Dispersive X-ray Spectroscopy (EDS) analysis were performed from an EDAX
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33 microanalysis. For the ICP-OES Pb(II) measurements a Thermo Scientific, model 6000
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Series equipment was used.
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38
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40 2.3. Preparation of the modified carbon paste electrode
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42 The carbon paste electrode modified with biochar (BchCPE) was prepared by
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carefully mixing the dispersed graphite powder (45–75% (w/w)) (Fischer), with biochar
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47 (0–30% (w/w)) and mineral oil (25% (w/w)). The components were mixed manually in a
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49 mortar and pestle for at least 10 min to obtain an appropriate homogenization.
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51 Subsequently, the modified carbon paste was packed into piston-driven electrode
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53 holder (PVC cylindrical tube, i.d. 3.0 mm) and arranged with a copper wire serving as
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56 an external electric contact. The electrode surface was smoothed by polishing on a
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58 piece of paper. For the carbon paste electrode modified with biochar and bismuth
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60 nanostructures (nBi-BchCPE) preparation, the carbon paste electrode modified only
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with biochar (BchCPE) was placed in 10 mL of Bi(III) ions solution for 30 s under no
1
2 applied potential and stirring conditions.
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2.4. Measurement procedure
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9 The voltammetric measurements were performed by adsorptive stripping
10
11 voltammetry. For pre-concentration step, the nBi-BchCPE was immersed in a stirred 10
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13 mL of 0.01 mol L-1 acetate buffer solution (pH 6) containing Pb(II) for 5 minutes at open
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circuit potential. The electrode was then removed from the pre-concentration cell,
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18 gently rinsed with 0.01 mol L-1 acetate buffer, placed in the electrochemical cell
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20 containing 10 mL of a quiescent supporting electrolyte (0.01 mol L-1 acetate buffer pH
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22 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-
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24 1
) for 30 s. After that, the voltammograms were recorded by applying a potential scan
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27 from −0.8 to +0.5 V under differential pulse voltammetry conditions with potential
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29 amplitude of 100 mV, pulse time of 25 ms and step potential of 5 mV. Finally, the
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31 electrode surface was renewed by mechanical polishing in paper.
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2.5. Analysis of real samples
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38 The leaching of Pb(II) present in these dishes was performed according to
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40 methodology adapted from ANVISA [37]. For the release test, it was used 0.1 mol L-1
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42 acetic acid solution for 2 hours at a temperature of 80°C. An aliquot of the resulting
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solution was added to the pre-concentration solution so that the concentration of Pb(II)
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47 stays within the linear range of techniques. Six brands of Chinese (porcelain / ceramic)
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49 dishes were evaluated with the techniques of DPAdSV (using the nBi-BchCPE) and
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51 ICP-OES.
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56 3. Results and discussion
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58 3.1. Voltammetric performance of Bi-BchCPE for Pb(II) determination
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The addition of the modifiers (biochar and bismuth) in the carbon paste aims to
1
2 improve the adsorption and, consequently, the detectability of Pb(II). To evaluate the
3
4 effect of the modifiers in the voltammetric response, the CPE, BchCPE and Bi-BchCPE
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were submitted to measurements after pre-concentration step in solution containing a
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9 10 µmol L-1 of Pb(II) ions. In Fig. 1A, the CPE presented a very low adsorption capacity
10
11 and negligible response. However, the signal observed for lead oxidation (Epa = - 0.57
12
13 V) using the BchCPE (Fig.1B) is remarkably higher than CPE which can be attributed
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to the presence of biochar in the paste due to phenomena such as metal exchange,
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18 complexation with functional groups, surface precipitation or physical adsorption that
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20 can significantly increases the pre-concentration of Pb(II) on the electrode surface [38].
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22 Finally the Fig. 1C represents the peak current of Pb(II) in Bi-BchCPE being
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24 remarkably greater than BchCPE, which clearly confirms the efficiency in the use of
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27 proposed sensor to the determination of Pb(II) due to the inherent advantages of the
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29 bismuth. Bismuth oxidation can be observed at potential of -0.10 V.
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31 Fig. 1
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3.2. SEM and EDS characterization of modified carbon paste electrodes
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38 The size and distribution of bismuth anchored on the BchCPE can affect
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40 significantly the determination of Pb(II). Fig. 2A shows a homogeneous dispersion of
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42 bismuth nanostructures (light gray spherical nanodots with some white agglomerates)
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44
on the biochar particles incorporated on the electrode surface which can be observed
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47 in detail in Fig. 2B. Fig. 2C shows the size distribution graph obtained by manual
48
49 counting of at least 500 structures, which indicates an average size of 42±3 nm. The
50
51 obtained bismuth nanostructures were manufactured and deposited on the electrode
52
53 surface by using an easier strategy in comparison with some other reported [22].
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56 To investigate the interaction between biochar, bismuth and lead, EDS
57
58 measurements were performed in BchCPE and nBi-BchCPE before and after pre-
59
60 concentration in solution containing 10 µmol L-1 of Pb(II) ions. For individual
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determination of lead and bismuth was necessary to investigate the less intense peaks
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2 of the layers Lα and Lβ for these metals in order to avoid signal overlap. A good
3
4 separation of these layers were obtained, with values of 10.51; 10.80; 12.56 and 12.97
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keV to Pb Lα, Bi Lα, PbLβ and Bi Lβ respectively. As can be seen in Fig. 2D, the
8
9 BchCPE (Fig 2D-Curve I) before pre-concentration of lead, the EDS spectrum has not
10
11 indicated the presence of any element which could interfere with the identification of
12
13 bismuth or lead. After pre-concentration of Pb(II) in BchCPE (Fig 2D-Curve II), it was
14
15
possible to observe the characteristic peaks of Pb Lα (10.51 keV) and Pb Lβ (12.56
16
17
18 keV). For nBi-BchCPE (Fig 2D-Curve III), before the pre-concentration of lead, it was
19
20 noted peaks of Bi Lα (10.80 keV) and Bi Lβ (12.97 keV) confirming the incorporation of
21
22 bismuth in the biochar. Finally, for nBi-BchCPE after pre-concentration and reduction of
23
24 Pb(II) (Fig 2D-Curve IV) the EDS spectrum taken from a nanodot has revealed the
25
26
27 presence of both Bi and Pb in the same nanostructure. These results confirm not only
28
29 the pre-concentration of analyte at the electrode surface but also they suggest strongly
30
31 the formation of alloy between lead with bismuth.
32
33 Fig. 2
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35
36
37
38 3.3. Influence of experimental parameters on the voltammetric response nBi-BchCPE
39
40 In order to obtain the best voltammetric behavior of the nBi-BchCPE for Pb(II)
41
42 determination, several parameters related to paste compositon, bismuth incorporation,
43
44
pre-concentration solution and operational parameters were examined in detail.
45
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47 The amount of biochar added in the nBi-BchCPE has a significative influence
48
49 on the voltammetric responses. Electrodes with different percentages of biochar were
50
51 prepared and examined for their voltammetric signals to Pb(II) under identical
52
53 conditions. The peak currents for Pb(II) have increased with increasing the amount of
54
55
56 biochar in the nBi-BchCPE due to the increased adsorption capacity of the electrode.
57
58 At 25% (w/w) of biochar the highest peak current was obtained. For amounts of biochar
59
60 higher than 25% the response of the nBi-BchCPE decreased due the reduction in
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conductivity of the modified electrode [39]. According to these results a carbon paste
1
2 composition of 25% biochar, 50% graphite and 25% mineral oil was used in further
3
4 studies.
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6
7
The presence of bismuth nanostructures on the electrode surface is
8
9 fundamental to its high sensitivity to the determination of Pb(II). For a fast and stable
10
11 incorporation of nano-bismuth the pH of the solution has great influence. In this way,
12
13 pH solutions ranging from 0.5 to 2.0 were used to study the grafting of Bi(III) ions on
14
15
the electrode surface. The maximum incorporation was achieved at pH 1.5, whereas at
16
17
18 low pH values a strong competion occurred between Bi(III) and H+ ions for adsorption
19
20 sites of biochar. At pH above 1.5, there is a spontaneous process of hydrolysis of
21
22 bismuth ions according to the reaction [40] Bi3+ + 3H2O  Bi(OH)3 + 3H+, limiting the
23
24 use of adsorption solutions of Bi(III) at pH values around 1.5.
25
26
27 The effect of the amount of bismuth added on the biochar was evaluated by
28
29 immersion of the electrode in the solution containing bismuth ions for different intervals
30
31 of time ranging from 15 to 300 s. After that, the electrode was submitted to pre-
32
33 concentration step in solution containing of 10 µmol L-1 Pb(II). As shown in Fig. 3, the
34
35
36
faradaic signals observed for oxidation of bismuth have increased with increase of time
37
38 suggesting an increase in the amount Bi(III) ions incorporated on the electrode surface.
39
40 By other side, the stripping peak height of Pb(II) (Fig. 3) increased with increasing time
41
42 of Bi(III) grafting from 15 to 30 s and it gradually decreases for values above 30 s
43
44
probably by formation of large clusters of nano-bismuth with consequent saturation of
45
46
47 adsorption sites of biochar. Therefore, the optimum time for Bi(III) incorporation was 30
48
49 s, which was chosen for following further experiments.
50
51 Fig. 3
52
53 The adsorption of Pb(II) on the surface of nBi-BchCPE occurs in the pre-
54
55
56 concentration solution and for efficient adsorption lead ions must be in their ionic free
57
58 form. So, the effect of pH for pre-concentration of Pb(II) at the electrode surface was
59
60 investigated in the range of 3.0 to 8.0. It was found that the peak current of Pb(II)
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62 8
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increased with increasing the pH reaching a maximum at pH value of 6.0 and
1
2 progressively decreased at higher pH values. At low pH values occurs the competition
3
4 between Pb(II) and H+ ions for the adsorption sites on the electrode. For high pH
5
6
7
values, the low response can be ascribed to the hydrolysis of lead [41, 42]. Therefore,
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9 the following experiments were carried out in pre-concentration solution with pH 6.0.
10
11 To evaluate the dependence between peak current and pre-concentration time,
12
13 Pb(II) ions were accumulated on the nBi-BchCPE using pre-concentration time varying
14
15
from 1 to 30 minutes. Anodic peak currents for Pb(II) have increased as the time pre-
16
17
18 concentration increases indicating a progressive increase in the amount of Pb(II)
19
20 adsorbed on the electrode. The peak currents start to stabilize after 15 minutes of pre-
21
22 concentration due to the equilibrium between ions in solution and those adsorbed on
23
24 the electrode surface. For further studies, an accumulation time of 5 minutes was used
25
26
27 in order to find a better combination between sensitivity and time of analysis.
28
29 In order to evaluate the effect of the composition of supporting electrolyte in the
30
31 voltammetric signal of Pb(II), phosphate buffer and acetate buffer solutions (both at pH
32
33 4.5) were studied. The best response was reached with measurements using acetate
34
35
36
buffer solutions due to the low tendency of formation of stable acetate-complexes with
37
38 Pb(II) being indicated by the stability constants for [Pb(Ac)]+ and [Pb(Ac)2], which are
39
40 reported as logK=2,68 and logK=4,08, respectively. These constants are significatively
41
42 lower than phosphate-Pb(II) species [PbHPO4] and [PbH2PO4]+, which have stability
43
44
constants of logK=15.48 and logK=21.07, respectively [40]. The influence of acetate
45
46
47 buffer concentration was studied in the range of 0.01 to 0.5 mol L-1 at pH 4.5 (controlled
48
49 ionic strength). Maximum peak current was obtained at 0.01 mol L-1 and a progressive
50
51 decrease for higher concentrations of acetate buffer solution was observed. Thus, a
52
53 supporting electrolyte consisting of 0.01 mol L-1 acetate buffer and 0.1 mol L-1 of KNO3
54
55
56 was selected for further studies.
57
58 The effect of pH of supporting electrolyte on the voltammetric responses of
59
60 Pb(II) was also studied for pH values between 2.0 and 7.0. Maximum peak current was
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62 9
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65
obtained at pH 4.5. At lower pH values the reduction in the magnitudes of voltammetric
1
2 signal can be attributed to replacement of Pb(II) pre-concentrated on the electrode
3
4 surface by H+ ions. For these reasons, the optimum pH of 4.5 was selected for
5
6
7
following experiments.
8
9 Beyond the general characteristics of the system above mentioned,
10
11 instrumental parameters can affect significantly the electrode response.The effect of
12
13 the reduction potential was studied in the range of −1.3 V to −0.6 V to the stripping
14
15
peak heights of Pb(II). The best result was obtained at -0.8 V since in more positive
16
17
18 potential values the reduction of Pb(II) become incomplete due to the proximity of the
19
20 redox potential of lead. For potential values more negative than -0.8 V there was a
21
22 gradual and slight interference of H+ ions in the reduction of lead. Reduction time
23
24 applied before voltammetric scan was investigated in the range of 0–120 s and it has
25
26
27 demonstrated a gradual increase in the response between 0 and 30 seconds, followed
28
29 by stabilization of current values over this time indicating that 30 s are enough for the
30
31 effective reduction of Pb(II) ions previously adsorbed. Based on these results, a
32
33 reduction potential of −0.8 V for 30 s was selected for further optimization studies.
34
35
36
37
38 3.4. Analytical performance of nBi-BchCPE
39
40 In order to obtain the best analytical performance for the proposed sensor,
41
42 calibration curves for Pb(II) were obtained by using of DPV, SWV and LSV under
43
44
optimal conditions (not shown). Table 1 shows the figures of merit of nBi-BchCPE for
45
46
47 each voltammetric technique used; the limit of detection (LOD) was estimated based
48
49 on three times the blank standard deviation divided by slope of the calibration curve
50
51 and the limit of quantification (LOQ) was calculated based on ten times the blank
52
53 standard deviation divided by slope of the calibration curve.
54
55
56 Table 1
57
58 Calibration curves obtained using DPV have shown a linear response for a
59
60 wider concentration range of Pb(II) ions in comparison with other voltammetric
61
62 10
63
64
65
techniques evaluated. From Table 1, it was observed that LSV had the poorer
1
2 analytical performance probably due to the high capacitive current present in their
3
4 measurements, which resulted in a low sensitivity and high LOD and LOQ. The SWV
5
6
7
showed the best sensitivity (151.64 µA L µmol-1) and an elevated noise in the
8
9 background current. For these reasons, considering the best LOD and LOQ, DPV
10
11 (under optimized conditions: step potential of 5 mV, pulse time of 25 ms and potential
12
13 amplitude of 100 mV) was selected for analytical applications.
14
15
In order to improve the analytical performance of the proposed sensor
16
17
18 calibration curves were constructed using pre-concentration time of 20 minutes under
19
20 DPV conditions (Fig. 4A and 4B). Fig. 4C shows a calibration plot that was linear over
21
22 the range concentration from 5.0 to 1,000 nmol L-1 for Pb(II). The linear regression
23
24 equation found was I (μA) = -1.27 + 82,02CPb(II) (where CPb(II) in µmol L-1). The LOD
25
26
27 obtained was 1.41 nmol L-1 and the LOQ was 4.70 nmol L-1.
28
29 Fig. 4
30
31 In comparison with a previously described Pb(II) sensor with biochar in the
32
33 absence of bismuth [35] the proposed sensor reaches a limit of detection (LOD) almost
34
35
36
10-fold better. The analytical features of the proposed electrode were compared (Table
37
38 2) with other bismuth modified electrodes previously reported in the literature for Pb(II)
39
40 determination. Moreover, the main advantage of the proposed sensor is the Pb(II) pre-
41
42 concentration performed at open circuit potential conditions that allows its use as a
43
44
passive sampler (especially for environmental applications) as well as the possibility of
45
46
47 rapid consecutive measurements after pre-concentration step.
48
49 Table 2
50
51 The intra-day reproducibility study of the nBi-BchCPE was carried out based on
52
53 the DPV response to 10 µmol L-1 Pb(II) pre-concentrated for 5 minutes using 5 different
54
55
56 electrode surfaces. The relative standard deviation (RSD) found was 3.40%,
57
58 demonstrating good reproducibility of the nBi-BchCPE, which can be attributed to a
59
60 good control of the carbon paste preparation and modification with biochar and
61
62 11
63
64
65
bismuth. For inter-day reproducibility study the same experiment was repeated by five
1
2 consecutive days indicating a RSD < 5.0%.
3
4
5
6
7
3.5. Effect of concomitants species
8
9 The influence of ionic species on the voltammetric responses was examined
10
11 using solution containing Pb(II) ions (concentration fixed at 2.40 µmol L-1) and foreign
12
13 ionic species at concentration levels based on limit established by CONAMA (Brazilian
14
15
legislation) [51].The evaluated species were considered as interfering agent when the
16
17
18 electrochemical signal for Pb(II) exhibited a deviation more than ±5.0%. It was
19
20 observed that the presence of species Ag+, As3+, Ba2+, Cd2+, Cl-, Cr3+, Cr6+, F-, Hg2+,
21
22 Mn2+, Ni2+, NO3-, Se4+, SO42- and Zn2+ had no interference in the voltammetric response
23
24 of Pb(II) even at high concentration level. A significant decrease in peak currents for
25
26
27 Pb(II) was observed when Cu2+ (10-fold), Fe3+(100-fold) and Sn2+(15-fold) were present
28
29 in the pre-concentration solution indicating that these metal ions compete with Pb(II) for
30
31 the binding sites of biochar. However, interference effect observed is constant and it
32
33 could be minimized by using of standard addition procedure.
34
35
36
37
38 3.6. Analyses in real samples
39
40 The nBi-BchCPE was applied to the analysis of Pb(II) released from overglaze-
41
42 decorated ceramic dishes. The solution used in the release test (0.1 mol L-1 acetic acid)
43
44
was added directly to the pre-concentration solution without any sample pre-treatment.
45
46
47 Concentrations of lead ions were determined by standard addition method and the
48
49 voltammetric results obtained were validated using ICP-OES. Fig. 5 presents the
50
51 Pb(II) concentrations measured by the proposed electrode and the corresponding
52
53 ICP-OES results. A good agreement was found between the values obtained by
54
55
56 nBi-BchCPE and ICP-OES, with deviations less than 5.0 %. Linear regression obtained
57
58 from the Fig.5 has given a value of R = 0.99941, a slope of 0.99475 and an intercept
59
60 with a value of 0.12561. In addition, the paired t-test (99% confidence level and 5
61
62 12
63
64
65
degrees of freedom) indicates that there are no significant differences between the
1
2 results obtained by the two methods. Therefore, these results demonstrate that the
3
4 proposed electrode can be successfully applied in the determination of Pb(II) in real
5
6
7
samples.
8
9 Fig. 5
10
11
12
13 4. Conclusions
14
15
16
17
18 The incorporation of bismuth nanostructures on biochar allowed the
19
20 development of a new modified carbon paste electrode, which has exhibited detection
21
22 limits of nmol L-1 for Pb(II) due to the high adsorptive capacity of biochar coupled with
23
24 electrochemical advantages of bismuth in nanoscale. It was also observed that the
25
26
27 proposed electrode had a linear reponse for a wide range of Pb(II) concentration,
28
29 excellent reproducibility and few interfering ions. Thus, the main features of nBi-
30
31 BchCPE are low cost, ease of fabrication, able to portability (due to pre-concentration
32
33 step in open circuit), quickness and high sensitivity in the analyses. Finally, the
34
35
36
analyses of Pb(II) released from overglaze-decorated ceramic dishes without any
37
38 sample pre-treatment, proved the efficiency of the proposed electrode and showed its
39
40 potential for fast, easy and sensitive monitoring of Pb(II) in various samples.
41
42
43
44
Acknowledgements
45
46
47
48
49 We gratefully acknowledge financial support from Brazilian foundations:
50
51 Fundação Araucária, CAPES, and CNPq.
52
53
54
55
56
57
58
59
60
61
62 13
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64
65
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1 LIST OF TABLES
2
3
4
5
6
7 Table 1
8
9
10
11
12
13 Table 1- Analytical performance for Pb(II) determination by DPV, SWV and LSV using
14
15 the proposed sensor.
16
17
18 DPV SWV LSV
19
20 -1
Linear range (nmol L ) 10 - 5000 50 - 1000 500 - 10000
21
22 -1
Sensitivity (µA L µ mol ) 29.61 151.64 3.80
23
24 Correlation coeficient 0.9997 0.9991 0.9995
25
26 -1
Limit of detection - LOD (nmol L ) 2.83 7.00 149
27
28 -1
29 Limit of quantification - LOQ (nmol L ) 9.43 23.3 495
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
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56
57
58
59
60
61
62 20
63
64
65
1
2
3
4
5 Table 2
6
7
8
9
10
11 Table 2- Comparison of present work and other bismuth modified electrodes for the
12
13 determination of Pb(II).
14
15
16 Electrode Technique LOD Linear range Ref.
17 -1 -1
18 (nmol L ) (nmol L )
19
20 µ-NP/BiFE DPAdSV 87 482.6 – 1930.5 [44]
21
22 BiFE SWASV 33 50–482.6 [45]
23
24 Bi-HA CME SWASV 24 50–965.3 [46]
25
26
Bi/poly(p-ABSA) film electrode DPASV 3.7 5 – 627.4 [47]
27
28
Bismuth modified carbon tape electrode SWASV 9.6 50 – 2413.1 [48]
29
30
31 BiFE SWASV 2.9 5 – 241.3 [49]
32
33 Bi-CNT electrode SWASV 6.3 9.6 – 482.6 [50]
34
35 nBi-BchDCPE DPAdSV 1.4 5 - 1000 This work
36 µ-NP/BiFE: micro/nanoparticle bismuth film electrode; DPAdSV: differential pulse adsorptive
37
38 stripping voltammetry; BiFE: bismuth film electrode; SWASV: square wave anodic stripping
39
40 voltammetry; Bi-HA CME: Bismuth-modified Hydroxyapatite Carbon Electrode; Bi/poly(p-ABSA)
41
42 film electrode: bismuth/poly(p-aminobenzene sulfonic acid) film electrode; Bi-CNT electrode:
43
44
bismuth-modified carbon nanotube electrode; nBi-BchDCPE: nano-bismuth modified biochar
45
46
doped carbon paste electrode.
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 21
63
64
65
1
2 CAPTIONS OF FIGURES
3
4
5
6 Fig. 1 – DPAdSV of 1.0 x 10-5 mol L-1 Pb(II) at (A) CPE, (B) BchCPE and (C) Bi-
7
8
9
BchCPE in 0.01 mol L-1 acetate buffer pH 4.5 + 0.1 mol L-1 KNO3. Reduction potential: -
10
11 0.8 V, reduction time: 30 s, potential scan: −0.8 to +0.5 V, potential amplitude: 100 mV,
12
13 pulse time: 25 ms, step potential: 5 mV. Pre-concentration step in 0.01 mol L-1 acetate
14
15 buffer pH 6 containing 10 µmol L-1 of Pb(II) ions for 5 min.
16
17
18
19
20
21
Fig. 2 - (A) SEM micrograph of nBi-BchCPE with magnification of 25 kx. (B) Detail of
22
23
24 bismuth nanosctructures in 132 kx. (C) Size distribution graph of bismuth
25
26 nanosctructures. (D) EDX pattern of BchCPE and nBi-BchCPE before and after Pb(II)
27
28 pre-concentration.
29
30
31
32
33
34 Fig. 3 – Effect of time of incorporation of Bi(III) ions on the anodic peaks (n = 3) current
35
36
37 for bismuth and Lead oxidation. Pre-concentration step in 0.01 mol L-1 acetate buffer
38
39 pH 6 containing 10 µmol L-1 of Pb(II) ions for 5 min (n = 3).
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44 Fig. 4 – DPV measurements under optimized conditions for Pb(II) using nBi-BchCPE.
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46
(A) Pb(II) concentration ranging from 0 – 1.0 µmol L-1; Pb(II) concentration ranging from
47
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49 0 – 0.1 µmol L-1; (C) Calibration plot (n = 3).
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55 Fig. 5 – Correlation plot for analysed samples using results obtained by proposed
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57 sensor and those provided by ICP-OES methodology.
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62 22
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Figure 1
Click here to download high resolution image
Figure 2A
Figure 2B
Figure 2C
Figure 2D
Figure 3
Figure 4
Figure 4
100
A 12 B 80 C
75
60
Iap / A
I / A
I / A
10
50 40
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
E / V vs. Ag/AgCl KCl 3 mol L CPb / mol L
2+
Figure 5

Tal D 15 00833R3

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Manuscript Number: TAL-D-15-00833R3

Article Type: Research Paper

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

Corresponding Author: Prof. Luiz Humberto Marcolino-Junior,

Corresponding Author's Institution:

First Author: Deonir Agustini

March, 15th, 2015.

determination of Lead released from ceramic dishes by using of bismuth nanostructures

determination of Lead ions released from ceramic dishes.

Thank you very much for your attention.

Dr. Luiz Humberto Marcolino-Junior

April 16th, 2015.

Prof. Dr. Jose Luis Burguera

Correspondence reference: TAL-D-15-00833R2

..traces of Lead ... should be: ...traces of lead ...

..reported by Suguihiro et al .... Should be: ....reported by Suguihiro et al. ....

..Oliveira et al .....it should be: ....Oliveira et al. ...

.Series equipment was used.... and not: ...Series equipmentwas used....

commas and dots was revised in a whole…

must be written the whole word).

Thank you in advance for your kind attention,

Dr. Luiz Humberto Marcolino-Junior

March, 15th, 2015.

a novelty in its use for Chemically Modified Electrode (CME) preparation;

 Narrow distribution of bismuth nanostructures size obtained by exploring of biochar

adsorption properties and improvement on the voltammetric stripping signal provided by

elevated Lead concentration into bismuth nanostructures;

and Selectivity) adequate when compared with others Electroanalytical methodologies;

comparison with ICP-OES methodology.

- Electrochemical procedure for growth of bismuth nanostructures

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

- 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.

0.1 mol L-1

Pb(II) released solutions

Sensitive voltammetric determination of lead released from ceramic

Sensitive voltammetric determination of lead released from ceramic

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