Journal of Electroanalytical Chemistry 799 (2017) 70–77

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Journal of Electroanalytical Chemistry

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

Determination of trace heavy metal ions by anodic stripping voltammetry MARK

using nanofibrillated cellulose modified electrode
K. Zinoubia, H. Majdouba, H. Barhoumia,⁎, S. Boufib, N. Jaffrezic-Renaultc
a
Laboratory of Interfaces and Advanced Materials, Faculty of Sciences, University of Monastir, Monastir, Tunisia
b
Laboratory of Material Sciences and Environment, Faculty of Sciences of Sfax, Tunisia
c
Laboratory of Analytical Sciences, Doua 69100 Villeurbanne, Lyon, France

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, nanofibrillated cellulose (NFC) has been used as a sensitive matrix to develop electrochemical
Nanofibrillated cellulose sensor trace heavy metal ions quantification via differential pulse anodic stripping voltammetry (DPASV).
Chemically modified CGE Cellulose fibers from Eucalyptus were fibrillated into nano-sized fibrils throughout the homogenization process.
DPASV To facilitate the fibrillation process, fibers were previously oxidized under neutral conditions to bring the
Heavy metal sensor
carboxyl content up to 500 μmol/g. NFC layer was deposited on a carbon glassy electrode (CGE) by simple
Seawater analysis
adsorption. The adopted DPASV method was achieved by optimizing some parameters such as the accumulation
time, the deposition time and the deposition potential. As a result, the modified electrode with nanofibrillated
cellulose exhibited reproducible response, high sensitivity and good stability for Cd(II), Cu(II), Pb(II) and Hg(II)
ions. The developed ion sensor was used for heavy metal determination in seawater.

1. Introduction
The rapid development of industries and the competitive use of
fresh water in many parts of the world cause the severe contamination
of water by heavy metals. The presence of heavy metals in industrial
effluents above the permitted level leads to serious environmental
pollution, threatening human health and the ecosystem [1]. Heavy
metal ions such as Cd(II), Cu(II), Pb(II) and Hg(II) ions, as well as
others, in small quantities play an important role in living organisms
existence which is essential for maintaining metabolism. However, even
very small doses or excessively high levels of toxic metals can cause
serious problems for human health and the environment. The accumu-
lation of these metals in the human body can cause diseases in the
central nervous system, liver, kidneys, skin, bones and teeth [2–4]
Hence, monitoring the concentration of these species in water bodies is
imperative in developing new strategies for the detection of heavy
metals [5–9]. Currently, various detection techniques have been
reported to quantify the trace of heavy metal ions, including electro-
chemical determination [10–14], atomic absorption spectrometry [15],
plasma-optical emission spectrometry [16], and fluorescence spectro-
metry [17]. However, spectrometric methods are expensive, cumber-
some, time consuming and unsuitable in situ measurements owing to
the required complex instrumentation. In contrast, electrochemical
techniques are attractive according to their remarkable sensitivity,
probability and low cost. Among the electrochemical methods, differ-
ential pulse anodic stripping voltammetry (DPASV) has been widely
deemed to a forceful technique for the quantification of heavy metal
ions due to an effective preconcentration process followed by electro-
chemical dissolution of the accumulated heavy metal ions [18–21].
Many electrochemical strategies are based on the modification of the
working electrode surface by chemicals reagents such as: monomole-
cular ligands [22–27], thiolamine [28,29], polymers [30–33]. In this
context, it is possible to use chemically modified electrodes with
renewable materials of miniaturized elements of plant origin [34].
Cellulose is the most abundant natural renewable and biodegradable
polymer. The main sources of cellulose fibers are annual plants and
wood with its two species namely hardwoods and softwoods. It exists in
a quasi-pure state in the form of cotton seed hair, but most often it is
found as being combined with other polysaccharides. By intelligent
processing techniques, they could be used as classical nanoreinforcing
elements in the fields of modified electrodes. They are organized in a
cellular hierarchical structure build up by bundles of thin microfibrils
aggregated into larger structures embedded into hemicellulose and
enclosed by lignin. The NFCs were produced by mechanically treating
cellulose suspensions through high pressure homogenizers. The typical
cross section of the nanofibrils ranges from 4 to 20 nm depending on
their origin, and each of them is formed by the association of many
cellulose molecules, which are linked together in repeating lengths

⁎
Corresponding author.
E-mail address: Houcine.Barhoumi@fsm.rnu.tn (H. Barhoumi).

http://dx.doi.org/10.1016/j.jelechem.2017.05.039
Received 26 March 2017; Received in revised form 13 May 2017; Accepted 23 May 2017
Available online 25 May 2017
1572-6657/ © 2017 Published by Elsevier B.V.
K. Zinoubi et al. Journal of Electroanalytical Chemistry 799 (2017) 70–77

along their chains. The NFCs present a jelly aspect with pseudo-plastic
properties [35].
In this study, we report the development of a modified glassy carbon
electrode (GCE) with nanocellulosic fibers for trace heavy metal ions
determination using differential pulse anodic stripping voltammetry
(DPASV).

2. Experimental

2.1. Chemicals and reagents

K4[Fe(CN)6]·3H2O, K3[Fe(CN)6], (KCl), CuCl2, Pb(NO3)2), CdSO4

and HgCl2 were purchased from Fluka Chemika. An acetate buffer
solution was prepared by adjusting 0.2 M of sodium acetate solution to
pH 4.5 with the addition of 0.2 M of acetic acid CH3COOH. This
solution was then further diluted with distilled water to give final
buffer strength of 0.1 M. The NFC material was fabricated by using
Eucalyptus pulp (eucalyptus globules) in the form of dry sheets.
Fig. 1. AFM observation of the CNF film.

2.2. Apparatus
150 GCE
The electrochemical measurements were performed using an NFC/GCE
Autolab (PGSTAT 302 N, Eco Chemie). All measurements were 100
performed in a dark Faraday cage. The electrochemical cell comprises
three electrodes: a platinum counter-electrode, an Ag/AgCl/KCl as 50
reference electrode and a glassy carbon (GC) as working electrode. Current/μA
AFM image was recorded in Tapping Mode using atomic force 0

microscopy IIIa digital instruments. Measurements were carried out at

-50
ambient atmospheric and temperature. The AFM probe was character-
ized by a spring constant of 12–103 N/m and a resonance frequency
-100
range of 200–400 kHz.
-150
2.3. Production of NFC
-200
Firstly, fibers were treated by TEMPO-mediated oxidation to gen- -0,2 0,0 0,2 0,4 0,6
erate carboxyl groups at a content of 500 μmol/g, in order to facilitate Potential/V(vs. Ag/AgCl)
the disintegration process. The oxidation was investigated at pH 10
Fig. 2. Cyclic voltammograms of modified and unmodified GCE in 0.1 M KCl solution
following the method reported previously [36]. Briefly, 2 g of cellulose
containing 5 mM [Fe(CN)6]3 −/4 − at scan rate of 100 mV s− 1.
fibers were suspended in 200 mL of water. Additional product such as
TEMPO (30 mg) and NaBr (250 mg) were mixed with the prepared
600
solution. Then, a solution of NaClO (50 mL) was added dropwise to the
cellulose suspension at a temperature around 5 °C, kept constant GCE
500 NFC/GCE
throughout the oxidation reaction. The pH of the mixture was adjusted
to 10 by addition of a 0.1 M of NaOH solution. After the washing step
400
with water to remove salt, a suspension of 1.5 wt% of prepared fibers
was homogenized in a high pressure homogenizer (NS1001L PANDA 2
K-GEA, Italy) applying six shear cycles (3 × 300 bar; 3 × 600 bar). A 300
-Z i(Ω)

thick transparent NFC gel was obtained after six passes.

200
2.4. Functionalization of the working electrode
100
The GCE was polished with alumina solution (0.5 μm), rinsed and
ultrasonicated in water for 3 min. Then, the GCE was scanned between 0
− 0.2 and 1.3 V in 0.5 M H2SO4 at 50 mV s− 1 for 10 cycles to remove
possible contaminations. Subsequently, 5 μL of NFC solution was 200 300 400 500 600 700 800 900 1000
deposited on the electrode. The modified surface was dried at ambient Z r (Ω)
temperature overnight. A good adhesion of the NFC film on the carbon
Fig. 3. Nyquist plots of modified and unmodified GCE in 0.1 M KCl solution containing
surface electrode was obtained. The high stability of the NFC/
5 mM [Fe(CN)6]3 −/4 −. Equivalent electrical circuit of the Nyquist plots.
Electrolyte interface can be attributed to the high adhesion of the
deposit NFC membrane on the carbon electrode surface. The long β-
chemical cell containing a three-electrode such as the modified GCE
glucans found in NF cellulose interact with the carbon surface through
(Ф = 3 mm) as working electrode, the Ag/AgCl/KCl as the reference
hydrogen bonding.
electrode and a platinum wire (Ф = 1 mm) as the counter electrode.
Acetate buffer solution as electrolyte support (0.1 M, pH = 4.5). The
2.5. Apparatus and electrochemical test procedure
accumulation of metal ions onto the NFCs film was performed at open
circuit by dipping the GCE/NFCs modified electrode during an accu-
The electrochemical measurements were carried out in an electro-

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K. Zinoubi et al. Journal of Electroanalytical Chemistry 799 (2017) 70–77

Table 1 3.2. Electrochemical characterization of NCFs/GCE

Electrochemical parameters of NFC/GCE and bare electrodes obtained from the analysis
impedance data with the Randle's circuit [R(C[RW])].
Cyclic voltammetry was investigated to check the change of the
Electrode Rs (Ω) Cdl (μF) Rct (Ω) W (μF) Ө electrode behavior after all modification steps. The electrochemical
results can prove the adsorption of the NFC matrix on the electrode
GCE 251.63 6.00 31.889 1666.3 – surface. In fact, electrode/solution interface behavior can be quantified
NFC/GCE 240.93 4.64 181.04 744.25 0.82
by cyclic voltammetry [34]. Fig. 2 shows the electroactivity change of
the [Fe(CN)6]3 −/4 − redox probe on the bare and the modified GC
mulation time of 20 min in stirred buffer solution for different metal ion electrode by the NFC matrix. The CV result of the bare GCE shows a
concentrations. After the accumulation step, the modified electrode was quasi-reversible redox signal, with a peak potential difference (ΔEp) of
washed carefully with ultrapure water. It was transferred to the 100 mV and a ratio of about 1:1 between anodic and cathodic peak
electrochemical cell containing 0.1 M acetate buffer solution. After currents, demonstrating that the glassy carbon electrode (GCE) has an
the preaccumulation step, the potential was held at − 0.9 V for 240 s interface reaction with [Fe(CN)6]3 −/4 − couple [38]. After the deposi-
under the static condition, followed by a positive going DPV scan with a tion of the NFC matrix the current decreases which demonstrates the
step increment of 5 mV and amplitude of 50 mV from − 1.2 to 0.5 V. functionalization process. To enhance the interface proprieties study
the electrochemical impedance spectroscopy (EIS) measurements were
used in order, to characterize the working electrode before and after the
3. Results and discussion modification process and to establish the interface equivalent circuit.
Impedance tests were performed in 0.1 M KCl solution containing 5 mM
3.1. Morphology of NFC film [Fe(CN)6]3 −/4 − over a frequency range of 0.1 Hz to 105 Hz. Fig. 3
shows an increase of the charge transfer resistance after the NFC film
Fig. 1 shows the NFCs film morphology, which is characterized by adsorption on the carbon glassy electrode surface. This result can be
cellulose nanofibrils having a typical width of 5–10 nm and lengths in explained by the blocking effect induced by the adsorbed organic layer
the micrometer range as confirmed from the AFM measurements. This which inhibits the charge transfer process. The Experimental EIS data
morphology is in agreement with our previous work, describing the were fitted using standard Randle's equivalent circuit [R(C[RW])]. The
production of CNFs from cellulose fibers [37]. proposed equivalent circuit was consisted of Rs, Rct, CPE and W which
represent the solution resistance, the charge transfer resistance, the

(a) (b)
18

16,8

16

16,4
Current/μA

14
Current/μA

16,0

12

15,6

10

15,2

8 (c)
3,5 4,0 4,5 5,0 5,5 6,0 5 10 15 20 25
pH Accumulation time (mn)

(c) (d)
17,0
16,8
16,8
16,6
16,6
16,4
16,4
Current/μA

16,2
Current/μA

16,2
16,0
16,0
15,8
15,8
15,6
15,6
15,4
15,4
15,2
15,2 15,0
-0,7 -0,8 -0,9 -1,0 -1,1 50 100 150 200 250 300

Potential/V (vs. Ag/AgCl) Preconcentration time (s)

Fig. 4. The effects of solution pH (a), accumulation time (b), deposition potential (c), deposition time (d) on the stripping currents of Cd(II) ions at NFC/GCE electrode in 0.1 M acetate
buffer solution containing 5.10− 8 M Cd(II) ions.

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K. Zinoubi et al. Journal of Electroanalytical Chemistry 799 (2017) 70–77

200
150
180 140
2+
160
Cd 130 Cu2+
120
140 110

120
100 k

Courant/μA
Courant/μA

90
100 80

80 70
60
60 50

40 40
30
20 20

0 10
0
-20 -10
-1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0 -0,3 -0,2 -0,1 0,0 0,1 0,2 0,3 0,4 0,5 0,6
Potential/V (vs. Ag/AgCl) Potential/V (vs. Ag/AgCl)
90
100

90
Pb2+ 80
Hg2+ a
80 70

70 60
Courant/μA

60 Courant/μA 50

50
40
40
30
30
20
20
10
10
0
0

-1,0 -0,8 -0,6 -0,4 -0,2 0,0 -0,1 0,0 0,1 0,2 0,3 0,4 0,5

Potential/V(vs.Ag/AgCl) Potential/V (vs. Ag/AgCl )

Fig. 5. Differential pulse anodic stripping voltammograms of Cd(II), Cu(II), Pb(II) and Hg(II) accumulated on the NFC/GCE electrode. (a) 10− 10 M, (b) 5.10− 10 M, (c) 10− 9 M, (d)
5.10− 9 M, (e) 10− 8 M, (f) 5.10− 8 M, (g) 10− 7 M, (h) 5.10− 7 M, (i) 10− 6 M, (j) 5.10− 6 M, (k) 10− 5 M, accumulation time 20 min in 0.1 M acetate buffer solution at pH 4.5, deposition
time 4 min and deposition potential − 0.9 V.

constant phase element related to the double layer capacitance (CPE)
and the Warburg impedance, respectively. The fitted electrochemical
parameters were gathered in Table 1.
From the Rct values, the apparent electrode coverage (Ө) of the NFC
deposition on the GCE area can be approximately calculated according
to the following Eq. (1) [39].
Ө = 1 − (R 0 tc / Rtc )
where Rct° and Rct are the charge transfer resistance before and after
GCE modification. The Rct is the value of each electrode surface during
modification, which is obtained with fitting of Nyquist plot of related
electrode surface. The results used for Eq. (1) are presented in Table 1.
According to the Nyquist plot, it was demonstrated that EIS variation
signal after NFC layer adsorption is equivalent to 82% of the covered
GC surface. In fact, when the modification of the GCE was established,
the EIS signal was equivalent to the formation of dense and packed
layer.
3.3. Optimization of experimental parameters
To obtain the best sensitivity of the deposit NFC sensing matrix
towards Cd(II), Cu(II), Pb(II) and Hg(II) ions quantification; the effect of
some parameters such as electrolyte pH, Accumulation time, deposition
potential and time were investigated. The experimental variables were
optimized as below.
3.3.1. Influence of pH
The pH of the metal ion solution has a significant effect on the
voltammetric behavior during the accumulation process. The working
pH effect on the sensor electrochemical response was studied in the pH
range from 3.5 to 6 by DPASV method. It was demonstrated as shown in
Fig. 4a that, the stripping peak currents was extensively affected by the
pH electrolyte variation. For example, we show the influence of the
(1) electrolyte pH variation on the Cd2 + accumulation on the NFC matrix.
A maximum DPASV peak current for Cd2 + was observed at pH around
4.5. The decrease of current at a pH lower than 4.5 can be explained by
the protonation process which affects the hydrophilic character of the
NFC matrix. The decrease of current at pH higher than 4.5 is attributed
to the hydrolysis of Cd2 + ions. Therefore, all electrochemical measure-
ments for different tested metal ions were carried out in 0.1 M acetate
buffer solution at optimal pH of 4.5.
3.3.2. Accumulation time
The accumulation time can affect the electrochemical performances
when the NFC matrix interacts with metallic ions. For this reason, the
accumulation time of the stripping reaction was optimized in the range
from 5 to 25 min. Fig. 4b shows that the optimal time of accumulation
was about 20 min.
3.3.3. Deposition potential
The deposition potential was tested in the range from −0.7 V to
− 1.1 V. As shown in Fig. 4c an optimal pre-concentration potential of
− 0.9 V was obtained which is characterized by the maximum current.

73
K. Zinoubi et al. Journal of Electroanalytical Chemistry 799 (2017) 70–77

200
140 2+
Cd 180
Cu2+
120 160

y = 55.88 x 140 y = 71.69 x

100 2
R = 0.9998 2
120 R = 0.9994

Current/ μA
Current/ μA

80
100

60 80

60
40

40
20
20

0
0

5,0 5,5 6,0 6,5 7,0 7,5 5,0 5,5 6,0 6,5 7,0 7,5
2+ 2+
-Log[Cu ] -log[Cd ]

80 2+
Pb 70
2+
70
60
Hg
y = 27.42 x
2 y = 24.55 x
60 R = 0.9978 2
50 R = 0.9980
Current/ μA

50
Current/ μA

40

40
30

30
20

20
10
10

0
5,0 5,5 6,0 6,5 7,0 7,5 5,0 5,5 6,0 6,5 7,0 7,5
-log[Pb2+] -Log[Hg ]
2+

Fig. 6. Calibration curves of the NFC/GCE electrode for different concentrations of Cd(II), Cu(II), Pb(II) and Hg(II) ions.

Table 2
Comparison of some characteristics of the different electrodes for the detection of Cd(II), Cu(II), Pb(II) and Hg(II).

Electrode Method Analyte Detection limit Sensitivity Reference

Au/GO/cysteamine SWASV Hg(II) 5 nM 11.4 nA·nM− 1 [41]

SPE/GO SWASV Cu(II) 37.2 nM 2.15 nA·nM− 1 [42]
GCE/GO/MWCNTs/Bi DPASV Cd(II) 5 nM 0.23 μA/μg L− 1 [43]
Pb(II) 1 nM 0.19 μA/μg L− 1
GCE/CN-polymer DPASV Cd(II) 2,27 μM 2.53 μA/mg L− 1 [44]
Pb(II) 0,8 μM 3.67 μA/mg L− 1
GCE/Polyaniline/Bi SWASV Cd(II) 1.1 nM 0.267 μA·nM− 1 [45]
Pb(II) 16,5 nM 0.268 μA·nM− 1
CPE/Fe3O4/CPE SWASV Cd(II) 47 nM 0.038 μA·μM− 1 [46]
Cu(II) 30 nM 0.014 μA·μM− 1
Hg(II) 10 nM 0.005 μA·μM− 1
GCE/GO/Fe3O4 SWASV Cd(II) 8 nM 14.87 μA·μM− 1 [47]
Pb(II) 6 nM 19.13 μA·μM− 1
Hg(II) 4 nM 24.19 μA·μM− 1
GCE/NFC DPASV Cd(II) 5 nM 71.69 μA·μM− 1 This work
Cu(II) 0.5 nM 55.88 μA·μM− 1
Pb(II) 0.5 nM 27.42 μA·μM− 1
Hg(II) 5 nM 24.55 μA·μM− 1

GCE: glassy carbon electrode, CPE: carbon paste electrode, GO: graphene oxide, SPE: screen printed electrode, NFC: nanofibrillated cellulose, CN-polymer: cyano groups modified poly
(diphenylamine co-2-aminobenzonitrile).

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K. Zinoubi et al. Journal of Electroanalytical Chemistry 799 (2017) 70–77

GCE Cu 2+ Table 4
140
NFC/GCE Pb 2+ The results of the recovery experiment.

120 Samples no. Cu(II) concentration (nM) Hg(II) concentration (nM)

100 Cd 2+ Added Found Recovery % Added Found Recovery %

Current/μA

80 1 – 63 – – 74 –
2 65 67 103 80 85 103.7
2+
60 Hg 3 70 69 98.5 90 91 101.1
4 75 79 105.3 95 97 102.1
40 5 80 83 103.7 100 100 100
(b)
20 (a)
3.3.4. Deposition time
0 The deposition time represents a decisive factor which can affect the
detection limit and the sensitivity of the sensing NFC membrane. The
-1,4 -1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0 0,2 0,4 0,6
deposition time was optimized using fixed Cd2 + ion concentration
Potential/V (vs. Ag/AgCl) (10− 8 M) in the time range from 30 to 210 s (Fig. 4d). When the
Fig. 7. Differential pulse anodic stripping voltammograms for simultaneous determina-
deposition time increases from 60 to 300 s, we observe a high increase
tion of (10− 5 M) Cd(II), Cu(II), Pb(II) and Hg(II) obtained at bare GCE (a), and NFC/GCE in current. However, the plot tended to be diminished slope value up to
(b). 240 s due to the rapid surface saturation. For this reason, 240 s was
chosen to be the optimal pre-concentration deposition time. The best
Table 3 working parameters were; pH 4.5, deposition time of 240 s at − 0.9 V
Stability of the sensor response during four weeks. and accumulation time 20 min for all metal ions.

Week Ion Sensitivity (μA·μM− 1)

1 Cu(II) 55.88 ± 0.50 3.4. DPASV analysis of Cd(II), Cu(II), Pb(II) and Hg(II)
Cd(II) 71.69 ± 1.61
Pb(II) 27.42 ± 0.33 Under the optimum conditions, Cd(II), Cu(II), Pb(II) and Hg(II) ions
Hg(II) 24.55 ± 0.97
were determined by DPASV method using the NFC nano-composite
2 Cu(II) 54.40 ± 1.02
Cd(II) 69.10 ± 1.20 sensing layer for different ion concentrations. Fig. 5 demonstrates that
Pb(II) 26.81 ± 0.70 the stripping peak currents of the tested metal ions increased subse-
Hg(II) 24.10 ± 0.98 quently with the metal ion concentration and stripping peaks towards
3 Cu(II) 53.75 ± 1.02 Cd(II), Pb(II), Cu(II) and Hg(II) appeared at potentials of − 0.8, −0.6, 0
Cd(II) 68.77 ± 1.30
Pb(II) 25.92 ± 0.65
and 0.3 V respectively.
Hg(II) 23.59 ± 0.82 Fig. 6 shows a linear characteristic with a correlation coefficient
4 Cu(II) 52.36 ± 1.12 nearby 0.999 obtained by plotting the current as function of the − Log
Cd(II) 66.82 ± 0.69 [ion]. Sensitivities of 71.7 μA·μM− 1, 55.8 μA·μM− 1, 27.4 μA·μM− 1 and
Pb(II) 24.33 ± 0.31
24.5 μA·μM− 1 were estimated for Cd(II) Cu(II), Pb(II) and Hg(II) ions in
Hg(II) 21.81 ± 0.33
dynamic concentration range, respectively. A low detection limit of
5 nM was obtained for Cd(II), Hg(II) and 0.5 nM for Cu(II) and Pb(II).
22 The analytical performances of the modified electrode for different
tested ions were a in good agreement with some responses reported for
20
other cited modified chemical electrodes (Table 2). Additionally, these
18 results exhibited lower detection limits of both Pb(II) and Cu(II)
compared to other carbon-based electrodes. In our work, high sensitiv-
16
ity were obtained by the proposed electrode for Cd(II), Cu(II), Pb(II),
Current/μA

14 80 nM and Hg(II) ions detection.

75 nM
12 70 nM 100 nM
65 nM 95 nM
10 0 nM 3.5. Interference study
90 nM
80 nM
8
0 nM After demonstrating the feasibility of the developed matrices for the
detection of some heavy metal ion, we investigated the technique for
6
potential use in the quantification of some heavy metal ions. In fact, the
4 potential for multi metal ion detection was demonstrated by the DPASV
-1,4 -1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0 0,2 0,4 0,6 voltammogram of NFC modified electrode after accumulation in a
Potential/V (vs. Ag/AgCl) mixture solution containing 10− 5 M of such ions (Cd(II), Cu(II), Pb(II),
and Hg(II)). The resulting voltammograms exhibited prominent and
Fig. 8. Differential pulse anodic stripping voltammograms for detection Cu(II) and Hg(II)
in sea water sample.
well as resolved peaks under the optimized parameters as shown in
Fig. 7. Notable and separated stripping peaks were observed for
different tested heavy metal ions accumulated on the carbon glassy
At this potential, the Cu(II) can preferentially adsorbed on the surface
electrode functionalized with the NFC layer. No current variation was
of the NFC modified electrode and the response signal is reduced due to
detected for the bare GCE treated under similar conditions. This current
the metal ion complexes during the anodic sweep. Far from this optimal
variation can be attributed to the high-affinity binding between the NFC
potential we note a shift in current because of the influence of hydrogen
layer and the accumulated metal ions.
evolution reaction (HER) [40].

75
K. Zinoubi et al.
3.6. Sensor stability and lifetime
To investigate the stability and lifetime of the developed ion sensor,
many modified electrodes were tested through a period of four weeks
and the results were reported in Table 3. During the specified duration
we observe weak deviation in sensitivity less than 3% with good
repeatability from prepared electrode to another. After its utilization
the NFC membrane can be easily regenerated using EDTA (Ethylene
diamine tetraacetic acid) solution to remove adsorbed heavy metal
ions.
3.7. Analysis of real sample
In order to evaluate the practical application of the NFC/GCE
electrode, the analytical performances were evaluated by measuring
the heavy metal ion activity in real water samples. The method was
applied to seawater samples to determine Cd(II), Cu(II), Pb(II), and Hg
(II) ions. The DPASV conditions were established under optimized
parameters such as initial potential −1.2 V, final potential 0.5 V and
amplitude of 50 mV. Furthermore, the DPASV response on real water
samples was also tested using Cu(II) and Hg(II) as a representation.
Taking the seawater as an example, Fig. 8 showed that there were
obvious signals in water samples which can be attributed to Cu(II) and
Hg(II) ions. Moreover, when Cu(II) and Hg(II) ions were added in the
seawater sample for different concentrations, resolved current peaks
were observed at − 0.2 V and 0.1 V. In addition, as shown in Table 4,
the good results of recovery experiment are obtained and the recoveries
are estimated to be near 98.5 towards 105.3%. Consequently, the
obtained results demonstrated that the developed sensing NFC matrix
can be as a suitable the potential applicability in environmental
monitoring. In this work the adopted electrochemical method is simple,
rapid, sensitive and less costly as compared to other analytical methods
like atomic absorption spectroscopy (AAS) and Inductively coupled
plasma optical emission spectrometry (ICPOS).
4. Conclusion
In this study an electrochemical sensor based on new sensing NFC
matrix for the quantification of trace Cd(II), Cu(II), Pb(II), and Hg(II)
was developed. The NFC/GCE modified electrode exhibits high sensi-
tivity, selectivity, good stability and low detection limit of 0.5 nM.
Among the tested ions, the higher sensitivity and the lower detection
limit was obtained for Cd(II) ion, which can be attributed to the better
affinity of Cd(II) to the NFC layer. It was demonstrated that NFC
modified electrode provides an alternative new strategy for the
electrochemical quantification of heavy ions. Under optimized working
conditions the Cd(II), Cu(II), Pb(II), and Hg(II) concentration in sea-
water samples has been successfully quantified. These features demon-
strate that the NFC/GCE ion sensor with excellent analytical perfor-
mances towards heavy metal ions could be served in future for efficient
application in real water samples.
Acknowledgements
The authors would like to thank CAMPUS-FRANCE for its support
through PHC Maghreb No. 12MAG088.
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