Accepted Manuscript

A novel electrochemical sensor based on a glassy carbon electrode modified with

dendrimer functionalized magnetic graphene oxide for simultaneous determination of
trace Pb(II) and Cd(II)

Mehdi Baghayeri, Heshmatollah Alinezhad, Maryam Fayazi, Mehrasa Tarahomi,

Reza Ghanei-Motlagh, Behrooz Maleki
PII: S0013-4686(19)30886-2
DOI: https://doi.org/10.1016/j.electacta.2019.04.180
Reference: EA 34128

To appear in: Electrochimica Acta

Received Date: 1 December 2018

Revised Date: 25 April 2019
Accepted Date: 28 April 2019

Please cite this article as: M. Baghayeri, H. Alinezhad, M. Fayazi, M. Tarahomi, R. Ghanei-Motlagh, B.
Maleki, A novel electrochemical sensor based on a glassy carbon electrode modified with dendrimer
functionalized magnetic graphene oxide for simultaneous determination of trace Pb(II) and Cd(II),
Electrochimica Acta (2019), doi: https://doi.org/10.1016/j.electacta.2019.04.180.

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 ACCEPTED MANUSCRIPT

Graphical Abstract

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A novel electrochemical sensor based on a glassy carbon electrode

modified with dendrimer functionalized magnetic graphene oxide
for simultaneous determination of trace Pb(II) and Cd(II)

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Mehdi Baghayeria,*, Heshmatollah Alinezhadb, Maryam Fayazic, Mehrasa Tarahomib,

Reza Ghanei-Motlaghd, Behrooz Malekia

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a
Department of Chemistry, Faculty of Science, Hakim Sabzevari University, P.O. Box 397, Sabzevar, Iran
b
Faculty of Chemistry, University of Mazandaran, P.O. Box 47416-95447, Babolsar, Iran
c
Department of Environment, Institute of Science and High Technology and Environmental Sciences,
Graduate University of Advanced Technology, Kerman, Iran

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Department of Clinical Sciences, Faculty of Veterinary Medicine, Shahid Chamran University of Ahvaz,
Ahvaz, Iran
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*Corresponding author;
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Mehdi Baghayeri: Tel: +98 5144013325, E-mail address: m.baghayeri@hsu.ac.ir

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Abstract

In this work, a glassy carbon electrode (GCE) coated with poly(amidoamine) dendrimer

functionalized magnetic graphene oxide (GO-Fe3O4-PAMAM) was applied for the simultaneous

detection of Pb(II) and Cd(II) in environmental waters. The square wave anodic stripping

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voltammetry (SWASV) method was employed for the determination of target metal ions after

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closed-circuit mode. The effects of different experimental variables such as supporting

electrolyte type, preconcentration solution pH, accumulation potential, accumulation time and

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concentration of dropped GO-Fe3O4-PAMAM nanocomposite were investigated and optimized.

At optimal chemical and electrochemical conditions, the designed sensor showed linear

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voltammetric responses in the ranges of 0.4-120 µg L-1 for Pb(II) and 0.2-140 µg L-1 for Cd(II)
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with coefficients of determination higher than 0.99. Low detection limits of 130 ng L-1 for Pb(II)

and 70 ng L-1 for Cd(II) were also achieved. Beside, possible interferents of some metal ions
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including Tl(I), Cu(II), Zn(II), Hg(II), Co(II), Mg(II), Ca(II), Mn(II), Ni(II), Fe(III), In(III) and
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Cr(III) were examined but did not cause any significant interferences. Finally, the present assay
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was employed for the simultaneous detection of both cations in real water samples, and the

obtained results were verified by inductively coupled plasma mass spectrometry (ICP-MS) as a
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confirmatory method.
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Keywords: Cadmium(II); Lead(II); Dendrimer; Simultaneous determination; Stripping

voltammetry

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1. Introduction

The possibility of simultaneous monitoring of trace heavy metal ions (e.g., Hg(II), Pb(II), Cd(II),

Cu(II), etc.) in environmental samples, mainly in water bodies, is nowadays an area of major

concern [1, 2]. Due to the increased industrial applications of heavy metals and their serious

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environmental impact, development of sensitive, selective and rapid measuring techniques is

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necessary and challenged. Nowadays, different analytical methods have been introduced for the

determination of heavy metals including inductively coupled plasma mass spectrometry (ICP-

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MS) [3], inductively coupled plasma optical emission spectrometry (ICP-OES) [4], atomic

absorption spectrometry (AAS) [5] and fluorescence spectrometry [6]. Such systems, however,

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require high implementation and maintenance costs. Electrochemical sensing techniques may
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provide an attractive alternative because of the low-cost instrumentation, excellent sensitivity,

good selectivity, ease of portability and simultaneous determination of heavy metal ions [7].
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Among various electroanalytical techniques, anodic stripping voltammetry (ASV) has been
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widely applied as an effective method for quantifying of heavy metals owing to efficient
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accumulation step and advanced electrochemical measurements of the preconcentrate target

metal ions in stripping step [8]. The performance of ASV method is strongly depends on the
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electrode modification materials [9]. Electrode modification usually utilized to improve the

conductivity, selectivity, sensitivity, stability and surface area of working electrodes [10].
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Accordingly, studies on electrochemical sensors based on novel materials with high efficiency
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towards trace detection of heavy metals are of great importance [11].

Among different materials for modification of the electrode surface, nanosized transition-metal

oxides (e.g., Fe3O4, Fe2O3, MnO2, Co3O4, etc.) have been employed for construction of heavy

metals sensor due to their unique structural property, high surface-to-volume ratio, notable

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electrocatalytic activity and high adsorption capability [12-15]. However, the use of metal oxide

nanostructures for stripping voltammetric analysis of heavy metal ions show some disadvantages

including low accessible adsorption sites, modifier leakage, and agglomeration of nanoscaled

inorganic materials during an electrochemical analysis. To conquer the obstacles, some carbon

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materials including carbon nanotubes (CNTs), graphene oxide (GO) and reduced graphene oxide

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(RGO) have been employed to stabilize these nanostructured metal oxides [16]. Among various

carbon materials, graphene with a two-dimensional structure has caused extensive attention due

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to its high specific area, unique electrical conductivity, self-assembly behavior and mechanical

flexibility [17]. Ultrathin graphene nanosheets provide a platform for the rapid diffusion of

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electrolyte, facilitating the interfacial charge transfer during the electrochemical reactions [18].
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On the other hand, chemical modification of graphene surface by organic and inorganic

compounds has been recognized as an effective method to improve the selectivity and adsorption
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capacity of the modified electrodes [19].

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Among different organic modifiers, macrocyclic chelators have also been applied in stripping
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voltammetric analysis of heavy metal ions due to their selective receptor properties and

feasibility for structural modification [20]. Dendritic macromolecules (dendrimers) have been
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proven to be suitable host templates because of the presence of multiple binding sites [21].

Among various dendrimers, poly(amidoamine) (PAMAM) dendrimers are more promising for
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the extraction of heavy metal ions from water because of the structural homogeneity and multiple
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functional surface terminal groups [22]. Although PAMAM dendrimers show elevated

selectivity to some heavy metals, the use of them in the electrochemical analysis has received

little attention, presumably due to their non-conductive properties.

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The strategy presented here is based on the combination of prominent electronic properties of

GO nanosheets, high adsorption capability of Fe3O4 nanoparticles and proper selectivity of NH2-

riched PAMAM dendrimer to design a novel voltammetric sensor for simultaneous detection of

Pb(II) and Cd(II). The electrochemical data demonstrated that the proposed sensor can be

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determined trace levels of both metal ions at concentrations lower than the guideline cadmium (5

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µg L-1) and lead (15 µg L-1) values in drinking water set by the U.S. Environmental Protection

Agency (USEPA) [23, 24]. The present method shows several advantages such as operation

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simplicity, remarkable selectivity, good sensitivity, and anti-interference performance.

2. Experimental
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2.1. Chemicals and materials

Ferrous chloride tetrahydrate (FeCl2 4H2O), ferric chloride hexahydrate (FeCl3 6H2O), sodium
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acetate (NaAc), acetic acid (HAc), ammonium hydroxide (NH4OH, 25%, w/w) were purchased
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from Merck (Darmstadt, Germany). Cd(II) and Pb(II) atomic absorption standard solutions (1000
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mg L-1 in 2% HNO3), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC)

and N-hydroxysuccinimide (NHS) were obtained from Sigma-Aldrich (St. Louis, MO, USA).
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GO was synthesized from graphite powder (Merck) by a modified Hummers method [25]. The

PAMAM dendrimer with 10-NH2 terminal groups was prepared according to the procedure
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published by Alinezhad et al. [26]. All other chemicals were of analytical grade and used as
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received. The supporting electrolyte was 0.1 mol L-1 acetate buffer solution and prepared via

HAc and NaAc. Ultra-pure water (18.2 MΩ cm) was used for the preparation of all aqueous

solutions.

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2.2. Apparatus

Fourier transform infrared spectroscopy (FT-IR) spectra were compared with the use of a Bruker

Equinox 55 spectrometer (Bruker, Karlsruhe, Germany). Powder X-ray diffraction patterns of the

samples were recorded on a PANalytical Empyrean X-ray diffractometer (Almelo, Netherlands)

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with a Cu-Kα radiation (λ=0.15418 nm). Scanning electron microscope (SEM) images and the

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energy-dispersive X-ray (EDX) spectroscopy analyses were taken using MIRA3 LM TESCAN

microscope (Brno, Czech Republic). Magnetizable measurements were carried out by a vibration

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sample magnetometer (VSM) (Meghnatis Daghigh Kavir Co., Kashan, Iran). The determination

of cadmium and lead in real samples were performed on an ICP-MS instrument (X Series 2,

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Thermo Scientific, Hemel Hempstead, UK) equipped with Ni cones and a glass concentric
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nebulizer (Meinhard, 1.0 mL min-1).

Square wave anodic stripping voltammograms (SWASVs) were obtained on an electrochemical

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computer-controlled workstation Palm-Sens (Palm Instrument BV, The Netherlands) monitored

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with PS Trace software. A one-compartment electrochemical cell consisting of a bare or

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modified glassy carbon electrode (MGCE) as working electrode, a platinum wire as counter

electrode, and an Ag/AgCl (3 mol L-1 KCl) electrode as reference electrode was applied for
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electrochemical tests.

2.3. Preparation of the GO-Fe3O4-PAMAM nanocomposite

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The GO/Fe3O4 nanocomposite was prepared via co-precipitation method. In a typical synthesis,
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60 mg of GO was dispersed in 20 mL of deionized water for 15 minutes and then heated to 50

°C. Subsequently, 160.0 mg of FeCl2·4H2O and 432.0 mg of FeCl3·6H2O was added into this

solution and dissolved with sonicator under N2 atmosphere. The mixture was dropwisely

alkalinized with 2 mL of aqueous NH4OH (25%) and then stirred for 40 min at 50 °C to

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complete the reaction. After cooling down at room temperature, the obtained product was

thoroughly washed with ultra-pure water and then collected magnetically.

The GO-Fe3O4-PAMAM was prepared according to the following procedure. Firstly, 150.0 mg

of GO/Fe3O4 was dispersed in 100 mL of water for a few minutes, and then 26.0 mg of EDC and

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7.5 mg of NHS were added under stirring at ambient condition. After activation of the carbonyl

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groups on GO/Fe3O4 composite, 1.5 mL of PAMAM dendrimer was added dropwise to the

mixture, and the reaction was allowed to proceed at ambient condition for overnight. Finally, the

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sediment was collected magnetically, washed with ethanol and then dried overnight in a vacuum

oven at 60 °C. The number of steps involved in the preparation of GO-Fe3O4-PAMAM is shown

in Scheme 1.
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2.4. Fabrication of the MGCE

In order to modify a GCE, 2.0 mg of the prepared GO-Fe3O4-PAMAM nanocomposite was

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dispersed in 2.0 mL of absolute ethanol under ultrasonic agitation to obtain a uniform

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suspension. Prior to coating, a GCE was polished with 0.05 µm Al2O3 powder slurries, and then
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sonicated in HNO3 aqueous solution (1.0 mol L-1), ultra-pure water and ethanol for 5 min,

respectively, to remove any adsorbed species on the electrode surface. Following that, 8 µL of
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GO-Fe3O4-PAMAM suspension (1.0 mg mL-1) dropped on the clean GCE surface and allowed to

evaporate solvent under room conditions.

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2.5. Electrochemical measurements

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SWASV was used for the determination of Cd(II) and Pb(II) on the MGCE. For this purpose, the

MGCE was inserted in a stirred 10 mL of acetate buffer (0.1 mol L-1, pH 4.5) and KCl (0.1 mol

L-1) solution containing a certain amount of Cd(II) and Pb(II). Accumulation of heavy metals on

the MGCE was acquired at a negative potential of -1.1 V (versus Ag/AgCl) for 160 s. At the end

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of the accumulation time, the stirring was switched off. After resting for 8 s, the square wave

voltammograms were recorded in the quiescent solution with pulse amplitude of 25 mV,

frequency of 15 Hz, and potential step of 4 mV. The MGCE was cleaned at 0.5 V for 120 s to

remove the residual metals under stirring condition. All electrochemical studies were carried out

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under a purified nitrogen atmosphere at room temperature (23±2°C). The experimental data were

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subjected to statistical analysis and are depicted as the mean ± standard deviation (SD).

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3. Results and discussion

3.1. Characterization of the GO-Fe3O4-PAMAM nanocomposite

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FT-IR spectra were obtained for GO, GO-Fe3O4, and GO-Fe3O4-PAMAM. Fig. S1(A) shows the
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FT-IR spectrum of GO. The broadband in the region 3000-3700 cm-1 can be assigned to the

stretching vibration of hydroxyl groups [27]. The characteristic peak at 1747 cm-1 is due to the
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C=O bonds and the peak at 1645 cm-1 is attributed to C=C bonds in un-oxidized graphitic
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domains [28]. Moreover, the absorption peak at around 1150 cm-1 represents the stretching
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vibration of alkoxy (C–O) groups [29]. These results confirm the existence of oxygen

functionalities in GO product. The FT-IR spectrum of GO-Fe3O4 (Fig. S1(B)) present new band
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at 609 cm-1 corresponding to Fe–O stretching vibration of Fe3O4 [30]. The typical characteristic

FT-IR peaks of GO-Fe3O4-PAMAM nanocomposite are depicted in Fig. S1(C). As seen,

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absorption bands from both components can be observed in the nanocomposite spectrum. In
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addition, the bands at 2863 and 2923-1 are attributed to the stretching vibrations of C–H in

PAMAM structure. The peak observed at 1465 cm-1 is assigned to the stretching vibration of C–

N bond in amide groups [31]. Moreover, the doublet at 1265 and 1217 cm-1 can be assigned to

the scissoring vibration of methylene in dendrimer molecules [32].

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The crystalline structures of GO, GO-Fe3O4 and GO-Fe3O4-PAMAM materials were investigated

via XRD measurements (Fig. S2). As it is visualized in Fig. S2(A), the diffraction peak of GO

shows a peak at a 2θ value of 10.86° corresponding to the (001) crystalline plane of GO sample

[33]. The XRD patterns of GO-Fe3O4 (Fig. S2(B)) and GO-Fe3O4-PAMAM (Fig. S2(C)) show

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six diffraction peaks at 2θ= 30.47° (220), 35.58° (311), 43.35° (400), 53.78° (422), 57.30° (511)

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and 63.05° (440) corresponding to cubic inverse spinel structure of Fe3O4 (JCPDS card No. 01-

075-0449) [34].

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The morphologies of GO, GO-Fe3O4, and GO-Fe3O4-PAMAM were evaluated by SEM analysis

as shown in Fig. 1. According to Fig. 1(A), GO presents a layer-like structure with the wrinkled

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edge. It is obvious (Fig. 1(B)) that the GO-Fe3O4 consists of a large number of nanoparticles
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which prove Fe3O4 was covered on the GO nanosheets. The combination of the GO with Fe3O4

nanoparticles and then, modification with PAMAM dendrimer, revealed a nanocomposite with
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the rough surface (Fig. 1(C)). Moreover, the higher degree of aggregation compared to the GO-
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Fe3O4 nanocomposite can be due to the modification of the GO-Fe3O4 with dendrimer molecules
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of PAMAM.

EDX analysis is applied to confirm the composition of the prepared materials. The EDX spectra
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of GO, GO-Fe3O4, and GO-Fe3O4-PAMAM are shown in Fig. S3(A-C). The EDX spectrum (Fig.

S3(C)) with the existence of carbon, oxygen, nitrogen, and iron elements also proved the
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successful functionalization of the GO-Fe3O4 nanocomposite with PAMAM dendrimer.

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The magnetic hysteresis loops of GO-Fe3O4 and GO-Fe3O4-PAMAM nanocomposite are

illustrated in Fig. S4. The saturation magnetization (Ms) value of GO-Fe3O4 was measured as

37.6 emu g-1, less than GO-Fe3O4-PAMAM nanocomposite (29. 7 emu g-1). The decrease of Ms

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value in GO-Fe3O4-PAMAM sample is ascribed to the modification of the GO-Fe3O4 with

PAMAM molecules.

3.2. Voltammetric behaviors of different modified electrodes

Before application of the GO-Fe3O4-PAMAM in the electrochemical detection of Pb(II) and

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Cd(II), the electrochemical surface area study was investigated. The cyclic voltammetric

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responses of different electrodes in the solution of 1.0 mmol L-1 K3Fe(CN)6/K4Fe(CN)6

containing 0.1 mol L-1 KCl are shown in Fig. S5(A). According to the Randles-Sevcik equation

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[35], the electrochemical surface areas for different electrodes including bare GCE, GO modified

GCE, GO-Fe3O4 modified GCE, GO-PAMAM modified GCE, and GO-Fe3O4-PAMAM

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modified GCE were found to be 0.025, 0.066, 0.091, 0.022 and 0.037 cm2, respectively. That is
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to say, the effective hybrid of Fe3O4 and GO may be conducive to provide an enhanced

electrochemical behavior, reflected by high peak currents and large electrochemical surface area.
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Moreover, the increased electrochemical surface area of GO-Fe3O4-PAMAM modified GCE

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compared to bare GCE indicates that GO-Fe3O4-PAMAM is beneficial to the improvement of

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the electrochemical performance and the adsorption of heavy metal ions.

Electrochemical impedance spectroscopy (EIS) has been widely employed as a powerful

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technique to investigate the interface features of modified electrodes [36, 37]. Fig. S5(B) shows

the Nyquist plots of bare electrode and four modified electrodes. As can be seen, the values of
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charge-transfer resistance (Rct) for different electrodes were obtained in the following order: GO-
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PAMAM modified GCE ˃ bare GCE ˃ GO-Fe3O4-PAMAM modified GCE ˃ GO modified GCE

˃ GO-Fe3O4 modified GCE. It can be seen that for GO-Fe3O4-PAMAM modified GCE, the

value of Rct increases compared to the GO-Fe3O4 modified GCE, suggesting that the GO-Fe3O4

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nanocomposite was successfully functionalized with PAMAM dendrimer. These results were

confirmed by cyclic voltammogram studies.

Initial SWASV studies were employed to evaluate the performance of the prepared

nanocomposite for detection of the target metal ions. Fig. 2 compares the SWASV responses

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obtained using bare GCE, GO modified GCE, GO-Fe3O4 modified GCE, GO-PAMAM modified

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GCE and GO-Fe3O4-PAMAM modified GCE in presence of 20 µg L-1 Cd(II) and 20 µg L-1

Pb(II). As seen, no distinct peaks were observed on the bare electrode in the potential range of -

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1.0 to -0.4 V (vs. Ag/AgCl). The response on the GO modified GCE was also poor for both metal

ions. In the case of GO-Fe3O4 modified GCE, the electrochemical signals are larger than that

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obtained with GO modified electrode. This is due to the high adsorption ability of magnetic
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nanoparticles in GO-Fe3O4 nanocomposite for Cd(II) and Pb(II) in accumulation step [38]. By

the addition of PAMAM to GO, the significant responses were observed at GO-PAMAM
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modified GCE. The improvement of peak currents at the GO-PAMAM modified GCE is mainly
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due to the multiple binding sites of PAMAM molecules for heavy target ions. The GO-Fe3O4-
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PAMAM modified GCE represented strong and well-defined signals for Cd(II) at -0.77 V and

Pb(II) at -0.54 V with the peak to peak separation of 230 mV. The increase in stripping currents
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mainly attributable to the high affinity of Fe3O4 and PAMAM in the GO-Fe3O4-PAMAM

nanocomposite for the target heavy metal ions. In addition, the potentials for the reoxidation of
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Pb(0) to Pb(II) on other modified electrodes are more negative than that observed on the GO-
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Fe3O4-PAMAM modified electrode, indicating that the reoxidation process is more favorable at

the GO-Fe3O4-PAMAM nanocomposite surface.

In order to exclude the effect of electrochemical active surface areas of different modifiers and

obtain the accurate results, a plot of current density versus concentration of analyte ions at

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different modified electrodes was researched. As seen in Fig. S6, the sensitivities of GO-Fe3O4-

PAMAM modified GCE towards Pb(II) and Cd(II) are larger than other modified electrodes such

as GO modified GCE, GO-Fe3O4 modified GCE, and GO-PAMAM modified GCE. By taking

into account of these results, the GO-Fe3O4-PAMAM modified GCE was employed for the

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simultaneous determination of trace Pb(II) and Cd(II) in the present study.

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3.3. Optimization of experimental conditions

In order to obtain the maximum sensitivity of the GO-Fe3O4-PAMAM nanocomposite electrode

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towards lead and cadmium ions, some important experimental parameters such as supporting

electrolyte type, preconcentration solution pH, concentration of dropped GO-Fe3O4-PAMAM,

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accumulation time and accumulation potential were evaluated in detail.
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Supporting solution is one of the critical parameters which influenced the performance of the

chemically modified electrode [39]. Thus, the effect of supporting electrolyte type on the
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electrochemical responses of the MGCE was studied by application of various buffer solution
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(0.1 mol L-1) including Britton-Robinson (B-R) universal buffer, phosphate buffer and acetate
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buffer at pH = 4.5. As depicted in Fig. S7(A), no obvious peaks obtained for the B-R and

phosphate buffer solutions. In contrast, the well-defined voltammetric peak shapes were acquired
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in acetate buffer solution for both metal ions. Furthermore, the sensitivity of the electrode was

elevated when KCl salt was added to the supporting electrolyte solution (Fig. S7(B)). Taking into
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consideration the above results, an acetate buffer solution with 0.1 mol L-1 KCl was selected in
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the whole study.

In order to explore the effect of the preconcentration solution pH on the sensitivity of the

proposed assay, typical SWASVs of the sensor towards cadmium and lead were obtained using

MGCE in 0.1 mol L-1 solutions of an acetate buffer containing of 0.1 mol L-1 KCl with adjusted

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pH values in the range of 3.0 to 6.0. As it is visualized in Fig. 3(A), the sensor responses

revealed a clear dependence on the solution pH as they increased with increasing pH up to 4.5,

and dropped down at higher pH values. The decrease in currents at pHs lower than 4.5 can be

explained on the basis of a directly competing between hydronium ions and the metal cations for

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active binding sites of the GO-Fe3O4-PAMAM. An increase in the pH (up to 4.5) leads to

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neutralization of the positive charge on the surface, which should increase the preconcentration

of target metals. In addition, the protonation degree of the amino groups decreased as the pH

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value increased, and the chelating ability of these primary and secondary amino groups for heavy

metal ions was enhanced [40]. On the other hand, the decrease in the anodic peak currents at pH

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values higher than 4.5 is attributed to hydrolysis of Pb(II) and Cd(II) [41]. An optimum pH of 4.5
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was chosen in the next stripping determinations. Moreover, it is noted that a moderately acidic

medium is satisfactory for the determination of Cd(II) and Pb(II) in aqueous samples [42, 43].
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GO-Fe3O4-PAMAM concentration had a remarkable influence on the sensitivity of the

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procedure. The effect of GO-Fe3O4-PAMAM concentration on the MCPE signals was

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investigated by casting different concentrations of dispersed GO-Fe3O4-PAMAM solution (0.2-

1.6 mg mL-1) on the GCE surface. As it is shown in Fig. 3(B), the modified electrode responses
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first increase with increasing the concentration of the modifier from 0.2 to 1.0 mg mL-1 and then

decreased upon further increase of the nanocomposite concentration up to 1.6 mg mL-1. This may
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tentatively be due to reduction of conductive area at the electrode surface. In all subsequent
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experiments, 1.0 mg mL-1 was used for the construction of the chemically modified electrode.

Accumulation potential is one of the factors that has a pronounced impact on sensitivity in

stripping analyses [44]. Hence, the effect of accumulation potential on the stripping signals was

examined in the potential range between -1.4 and -0.8 V (versus Ag/AgCl). As shown in Fig.

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3(C), the highest efficiencies of Pb(II) and Cd(II) accumulation could be achieved at -1.1 V for

lead and at -1.2 V for cadmium. The significant decrease in stripping peak currents at

accumulation potential less negative than -1.1 V is attributed to incomplete reduction of Pb(II)

and Cd(II) on the MGCE surface [45]. At higher potentials, the stripping current peak intensities

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reduced, caused by the hydrogen reduction at modified electrode surface [46]. The accumulation

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potential is finally set as -1.1 V to ensure simultaneous and efficient accumulation of both ion

species.

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Accumulation time is another critical factor for quantification of metal ions in stripping

voltammetry methods [47]. The effect of accumulation time on the analytical signal intensities of

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the MGCE was researched over different periods of time from 30 to 220 s (Fig. 3(D)). It is clear
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that the peak currents increase with increasing the accumulation time up to 160 s and tends to

reach steady at the higher accumulation time. Therefore, an accumulation time of 160 s was
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selected for all experiments in order to ensure the complete reduction of target ions on the
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MGCE. However, it should be mentioned that for the lowest concentrations of lead and cadmium
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ions longer accumulation time at modified working electrode is recommended.

3.4. Analytical features

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The optimal operational conditions (i.e., pH of 4.5 (0.1 mol L-1 HAc-NaAc + 0.1 mol L-1 KCl),

nanocomposite concentration of 1.0 mg mL-1, accumulation potential of -1.1 V, and

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accumulation time of 160 s) were considered for the evaluation of the linear concentration range
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(LCR), detection limit (DL) and reproducibility of the present method. Electrochemical

determinations of one analyte with different concentrations in the presence of a fixed

concentration of another target ion (20 µg L-1) are presented in Fig. 4(A) and Fig. 4(B). The

LCRs of 0.2-140 µg L-1 for Cd(II) and 0.4-120 µg L-1 for Pb(II) were obtained via the MGCE. In

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addition, the linear regression equations were I (µA) = 0.1885 (µA µg L-1) CCd (µg L-1) +3.7513

for Cd(II) and I (µA) = 0.155 (µA µg L-1) CPb (µg L-1) +1.4438 for Pb(II) with high coefficients

of determination >0.99. The DL was calculated according to the definition of IUPAC [48] based

on 3 times the standard deviation of 10 measurements of the blank solution. The DLs of this

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method for cadmium and lead were found to be 70 ng L-1 and 130 ng L-1, respectively. The DL

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values of the proposed electrochemical device are low enough to measure trace cadmium and

lead concentrations in water samples according to the USEPA guideline values. The performance

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of the MGCE for the simultaneous detection of Pb(II) and Cd(II) with increasing concentrations

of both ions is also depicted in Fig. 5. Comparing to the individual analysis, the LCRs and

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sensitivity of calibration curves for simultaneous detection of Cd(II) and Pb(II) remain almost
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unchanged. These results confirm that the present assay able to applied for the individual and

simultaneous detection of Cd(II) and Pb(II). The present procedure suggests good reproducibility
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with a relative standard deviation (RSD) values of 3.5% for Cd(II) and 4.0% for Pb(II) at eight
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individually prepared electrodes in a solution containing 20 µg L-1 of each ions. In addition, the
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repeatability was also evaluated by analysis of the mixed solution containing 20 µg L-1 Cd(II)

and Pb(II) with eight repetitive measurements at a single modified electrode. The RSD values for
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the stripping currents of Cd(II) and Pb(II) were found to be 1.7 and 2.1%, respectively. The

storage stability of the MGCE was studied over a 3 weeks period by daily monitoring the
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variation in its voltammetric current responses to 20 µg L-1 of target ions. In between

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measurements the sensor was kept at room temperature in the dry state. After storing for 3

weeks, the peak currents diminished gradually and retained 95.7% (for Pb(II)) and 96.3% (for

Cd(II)) of the initial responses, confirming the long term stability of the proposed sensor. The

analytical features of the present method for simultaneous determination of Pb(II) and Cd(II) are

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also summarized in Table 1. In addition, a comparison between the performance of the proposed

assay with some recently sensing methods [41, 49-60] for detection of Cd(II) and Pb(II) is

provided in Table 2. As seen, the DL value of the present method is superior to other modified

electrodes.

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3.5. Selectivity measurement and real sample analysis

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Multiple co-existed metal ions are frequently encountered within practical application of

electrochemical sensors [61]. To evaluate the anti-interference capabilities of the MGCE, some

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foreign ions including Tl(I), Cu(II), Zn(II), Hg(II), Co(II), Mg(II), Ca(II), Mn(II), Ni(II), Fe(III),

In(III) and Cr(III) were utilized as possible interfering species. The selectivity of the sensor was

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explored by calculating the peak current ratio (Is/I0), where Is and I0 were stripping peak
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responses of each target ions in the presence and absence of interfering species, respectively. As

shown in Fig. S8, a 650-fold excess of Mg(II), Ca(II), 350-fold excess of Co(II), Mn(II), Ni(II),
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Fe(III), 200-fold excess of Zn(II), Hg(II), Cr(III), In(III), 100-fold excess of Tl(I) and 75-fold
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excess of Cu(II) did not affect the electrochemical signals (the peak current changes were below
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5%) of 20.0 µg L-1 of analyte ions. In addition, to provide more information about the selectivity

behavior of the MGCE, sample SWASVs of Pb(II) and Cd(II) in the absence and presence of
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Cu(II) and Hg(II) were investigated. As can be seen in Fig. S9, no obvious change can be

observed on the GO-Fe3O4-PAMAM modified electrode though adding 200-fold concentration

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of mercury ions (Fig. S9(A)). However, the injection of 100-fold concentration of Cu(II) was
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found to suppress the peak current of Cd(II) (decreased by about 17.6%) and Pb(II) (decreased

by about 13.4%) (Fig. S9(B)). This phenomenon might be attributed to competition for

accumulation sites at the MGCE surface by the interfering copper ions. The selectivity studies

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indicate that the MGCE can be employed with confidence for monitoring of Pb(II) and Cd(II) in

real samples.

To explore the applicability of the proposed system, it was successfully used to measure Pb(II)

and Cd(II) in lake (Chalidarreh lake, Torghabeh, Iran) and river (Kardeh river, Mashhad, Iran)

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waters. The determined concentrations for both ions based on the MGCE and ICP-MS technique

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are given in Table S1. The amounts obtained for lake water sample were found to be 1.7 and 3.3

µg L-1, while for river water sample were 3.7 and 5.2 µg L-1 for Pb(II) and Cd(II), respectively.

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In addition, typical SWASVs of the MGCE in river water sample and different concentration of

metal ions in this water sample (standard addition method) are demonstrated in Fig. S10. It is

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evident that the suggested electrochemical sensor is capable to determine the concentration of
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both analyte ions in real water sample without any significant interferes and matrix problems.

The analytical data were also verified by ICP-MS as a confirmatory method. Moreover, recovery
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tests were conducted for metallic analytes and the recovery values of the spiked samples were
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close to 100.0%, ranging from 96.0 to 103.0% for lead and 96.7 to 104.0% for cadmium at
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admissible RSD values. These results confirm the analytical usefulness of the present method for

the quantification of Pb(II) and Cd(II) in environmental water samples.

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4. Conclusions

In summary, novel electrochemical sensing protocol based on the modification of a GCE with
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GO-Fe3O4-PAMAM nanocomposite was introduced for simultaneous detection of Pb(II) and

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Cd(II). Due to the good synergistic integration of the nanomaterials in the GO-Fe3O4-PAMAM

nanocomposite, the present electrochemical device demonstrated high sensitivity and good anti-

interference capability for analysis of analyte ions. The chemical and electrochemical factors that

exert an effect on accumulation and stripping of metal ions, including supporting electrolyte

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type, preconcentration solution pH, accumulation time, accumulation potential and concentration

of dropped nanocomposite were carefully investigated. Under optimal conditions, the DLs were

found to be at ng L-1 levels for both metallic ions which are well below than the drinking water

safe limits allowed by the USEPA. The applicability of the MGCE for measuring of lead and

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cadmium in real water samples was successfully studied. To conclude, the suggested method

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offers a new promising platform for simultaneous detection of Pb(II) and Cd(II).

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References

[1] Z. Khoshbin, M.R. Housaindokht, A. Verdian, M.R. Bozorgmehr, Simultaneous detection

and determination of mercury (II) and lead (II) ions through the achievement of novel functional

nucleic acid-based biosensors, Biosensors and Bioelectronics, 116 (2018) 130-147.

PT
[2] Y. Ma, Y. Wang, D. Xie, Y. Gu, X. Zhu, H. Zhang, G. Wang, Y. Zhang, H. Zhao,

RI
Hierarchical MgFe-layered double hydroxide microsphere/graphene composite for simultaneous

electrochemical determination of trace Pb(II) and Cd(II), Chemical Engineering Journal, 347

SC
(2018) 953-962.

[3] M. Shen, L. Chen, W. Han, A. Ma, Methods for the determination of heavy metals in

U
indocalamus leaves after different preservation treatment using inductively-coupled plasma mass
AN
spectrometry, Microchemical Journal, 139 (2018) 295-300.

[4] Y. Yamini, M. Safari, Modified magnetic nanoparticles with catechol as a selective sorbent
M

for magnetic solid phase extraction of ultra-trace amounts of heavy metals in water and fruit
D

samples followed by flow injection ICP-OES, Microchemical Journal, 143 (2018) 503-511.
TE

[5] V. Kazantzi, A. Kabir, K.G. Furton, A. Anthemidis, Fabric fiber sorbent extraction for on-

line toxic metal determination by atomic absorption spectrometry: Determination of lead and
EP

cadmium in energy and soft drinks, Microchemical Journal, 137 (2018) 285-291.

[6] J. Peng, J. Li, W. Xu, L. Wang, D. Su, C.L. Teoh, Y.-T. Chang, Silica Nanoparticle-
C

Enhanced Fluorescent Sensor Array for Heavy Metal Ions Detection in Colloid Solution,
AC

Analytical Chemistry, 90 (2018) 1628-1634.

[7] Y. Lu, X. Liang, C. Niyungeko, J. Zhou, J. Xu, G. Tian, A review of the identification and

detection of heavy metal ions in the environment by voltammetry, Talanta, 178 (2018) 324-338.

[8] J. Wang, Stripping analysis, Encyclopedia of Electrochemistry: Online, (2007).

19
 ACCEPTED MANUSCRIPT

[9] A. Afkhami, H. Khoshsafar, H. Bagheri, T. Madrakian, Construction of a carbon ionic liquid

paste electrode based on multi-walled carbon nanotubes-synthesized Schiff base composite for

trace electrochemical detection of cadmium, Materials Science and Engineering: C, 35 (2014) 8-

14.

PT
[10] H. Bagheri, A. Afkhami, H. Khoshsafar, M. Rezaei, S.J. Sabounchei, M. Sarlakifar,

RI
Simultaneous electrochemical sensing of thallium, lead and mercury using a novel ionic

liquid/graphene modified electrode, Analytica Chimica Acta, 870 (2015) 56-66.

SC
[11] A. Waheed, M. Mansha, N. Ullah, Nanomaterials-based electrochemical detection of heavy

metals in water: Current status, challenges and future direction, TrAC Trends in Analytical

Chemistry, 105 (2018) 37-51.

U
AN
[12] W.-J. Li, X.-Z. Yao, Z. Guo, J.-H. Liu, X.-J. Huang, Fe3O4 with novel nanoplate-stacked

structure: Surfactant-free hydrothermal synthesis and application in detection of heavy metal

M

ions, Journal of Electroanalytical Chemistry, 749 (2015) 75-82.

D

[13] S.-S. Li, W.-J. Li, T.-J. Jiang, Z.-G. Liu, X. Chen, H.-P. Cong, J.-H. Liu, Y.-Y. Huang, L.-
TE

N. Li, X.-J. Huang, Iron oxide with different crystal phases (α-and γ-Fe2O3) in electroanalysis

and ultrasensitive and selective detection of lead (II): an advancing approach using XPS and
EP

EXAFS, Analytical chemistry, 88 (2015) 906-914.

[14] Q.-X. Zhang, D. Peng, X.-J. Huang, Effect of morphology of α-MnO2 nanocrystals on
C

electrochemical detection of toxic metal ions, Electrochemistry Communications, 34 (2013) 270-

AC

273.

[15] Z.-G. Liu, X. Chen, J.-H. Liu, X.-J. Huang, Well-arranged porous Co3O4 microsheets for

electrochemistry of Pb (II) revealed by stripping voltammetry, Electrochemistry

Communications, 30 (2013) 59-62.

20
 ACCEPTED MANUSCRIPT

[16] L. Cui, J. Wu, H. Ju, Electrochemical sensing of heavy metal ions with inorganic, organic

and bio-materials, Biosensors and Bioelectronics, 63 (2015) 276-286.

[17] K.T. Paula, G. Gaál, G. Almeida, M. Andrade, M.H. Facure, D.S. Correa, A. Riul Jr, V.

Rodrigues, C.R. Mendonça, Femtosecond laser micromachining of polylactic acid/graphene

PT
composites for designing interdigitated microelectrodes for sensor applications, Optics & Laser

RI
Technology, 101 (2018) 74-79.

[18] D. Chen, H. Feng, J. Li, Graphene oxide: preparation, functionalization, and electrochemical

SC
applications, Chemical Reviews, 112 (2012) 6027-6053.

[19] S. Muralikrishna, K. Sureshkumar, T.S. Varley, D.H. Nagaraju, T. Ramakrishnappa, In situ

U
reduction and functionalization of graphene oxide with L-cysteine for simultaneous
AN
electrochemical determination of cadmium (II), lead (II), copper (II), and mercury (II) ions,

Analytical Methods, 6 (2014) 8698-8705.

M

[20] M. Ghanei-Motlagh, C. Karami, M.A. Taher, S.J. Hosseini-Nasab, Stripping voltammetric

D

detection of copper ions using carbon paste electrode modified with aza-crown ether capped gold
TE

nanoparticles and reduced graphene oxide, RSC Advances, 6 (2016) 89167-89175.

[21] E. Vunain, A. Mishra, B. Mamba, Dendrimers, mesoporous silicas and chitosan-based

EP

nanosorbents for the removal of heavy-metal ions: a review, International Journal of Biological

Macromolecules, 86 (2016) 570-586.

C

[22] A. Rether, M. Schuster, Selective separation and recovery of heavy metal ions using water-
AC

soluble N-benzoylthiourea modified PAMAM polymers, Reactive and Functional Polymers, 57

(2003) 13-21.

[23] M. Fayazi, M.A. Taher, D. Afzali, A. Mostafavi, M. Ghanei-Motlagh, Synthesis and

application of novel ion-imprinted polymer coated magnetic multi-walled carbon nanotubes for

21
 ACCEPTED MANUSCRIPT

selective solid phase extraction of lead(II) ions, Materials Science and Engineering: C, 60 (2016)

365-373.

[24] M. Ghanei-Motlagh, M. Taher, Novel imprinted polymeric nanoparticles prepared by sol–

gel technique for electrochemical detection of toxic cadmium (II) ions, Chemical Engineering

PT
Journal, 327 (2017) 135-141.

RI
[25] L.J. Cote, F. Kim, J. Huang, Langmuir− Blodgett assembly of graphite oxide single layers,

Journal of the American Chemical Society, 131 (2008) 1043-1049.

SC
[26] H. Alinezhad, A. Amiri, M. Tarahomi, B. Maleki, Magnetic solid-phase extraction of non-

steroidal anti-inflammatory drugs from environmental water samples using polyamidoamine

U
dendrimer functionalized with magnetite nanoparticles as a sorbent, Talanta, 183 (2018) 149-
AN
157.

[27] M. Ghanei-Motlagh, M.A. Taher, A. Heydari, R. Ghanei-Motlagh, V.K. Gupta, A novel

M

voltammetric sensor for sensitive detection of mercury(II) ions using glassy carbon electrode
D

modified with graphene-based ion imprinted polymer, Materials Science and Engineering: C, 63
TE

(2016) 367-375.

[28] N. Justh, B. Berke, K. László, L.P. Bakos, A. Szabó, K. Hernádi, I.M. Szilágyi, Preparation
EP

of graphene oxide/semiconductor oxide composites by using atomic layer deposition, Applied

Surface Science, 453 (2018) 245-251.

C

[29] F. Alotaibi, T.T. Tung, M.J. Nine, S. Kabiri, M. Moussa, D.N. Tran, D. Losic, Scanning
AC

atmospheric plasma for ultrafast reduction of graphene oxide and fabrication of highly

conductive graphene films and patterns, Carbon, 127 (2018) 113-121.

22
 ACCEPTED MANUSCRIPT

[30] M. Fayazi, M.A. Taher, D. Afzali, A. Mostafavi, Preparation of molecularly imprinted

polymer coated magnetic multi-walled carbon nanotubes for selective removal of

dibenzothiophene, Materials Science in Semiconductor Processing, 40 (2015) 501-507.

[31] X. Chen, Y. Wang, Y. Zhang, Z. Chen, Y. Liu, Z. Li, J. Li, Sensitive electrochemical

PT
aptamer biosensor for dynamic cell surface N-glycan evaluation featuring multivalent

RI
recognition and signal amplification on a dendrimer–graphene electrode interface, Analytical

Chemistry, 86 (2014) 4278-4286.

SC
[32] S. Chandra, K. Lokesh, A. Nicolai, H. Lang, Dendrimer-rhodium nanoparticle modified

glassy carbon electrode for amperometric detection of hydrogen peroxide, Analytica Chimica

Acta, 632 (2009) 63-68.

U
AN
[33] K.S. Lee, C.W. Park, S.J. Lee, J.-D. Kim, Hierarchical zinc oxide/graphene oxide

composites for energy storage devices, Journal of Alloys and Compounds, 739 (2018) 522-528.
M

[34] A. Hosseinifar, M. Shariaty-Niassar, S. Seyyed Ebrahimi, M. Moshref-Javadi, Synthesis,

D

characterization, and application of partially blocked amine-functionalized magnetic

TE

nanoparticles, Langmuir, 33 (2017) 14728-14737.

[35] T.A. Silva, H. Zanin, E. Saito, R.A. Medeiros, F.C. Vicentini, E.J. Corat, O. Fatibello-Filho,
EP

Electrochemical behaviour of vertically aligned carbon nanotubes and graphene oxide

nanocomposite as electrode material, Electrochimica Acta, 119 (2014) 114-119.

C

[36] M. Ghanei-Motlagh, M.A. Taher, A novel electrochemical sensor based on silver/halloysite

AC

nanotube/molybdenum disulfide nanocomposite for efficient nitrite sensing, Biosensors and

Bioelectronics, 109 (2018) 279-285.

23
 ACCEPTED MANUSCRIPT

[37] M. Ghanei-Motlagh, M.A. Taher, M. Fayazi, M. Baghayeri, A. Hosseinifar, Non-enzymatic

amperometric sensing of hydrogen peroxide based on vanadium pentoxide nanostructures,

Journal of The Electrochemical Society, 166 (2019) B367-B372.

[38] Y.-F. Sun, W.-K. Chen, W.-J. Li, T.-J. Jiang, J.-H. Liu, Z.-G. Liu, Selective detection

PT
toward Cd2+ using Fe3O4/RGO nanoparticle modified glassy carbon electrode, Journal of

RI
Electroanalytical Chemistry, 714 (2014) 97-102.

[39] A. Afkhami, H. Bagheri, H. Khoshsafar, M. Saber-Tehrani, M. Tabatabaee, A. Shirzadmehr,

SC
Simultaneous trace-levels determination of Hg(II) and Pb(II) ions in various samples using a

modified carbon paste electrode based on multi-walled carbon nanotubes and a new synthesized

U
Schiff base, Analytica Chimica Acta, 746 (2012) 98-106.
AN
[40] Y. Liu, L. Xu, J. Liu, X. Liu, C. Chen, G. Li, Y. Meng, Graphene oxides cross-linked with

hyperbranched polyethylenimines: preparation, characterization and their potential as recyclable

M

and highly efficient adsorption materials for lead (II) ions, Chemical Engineering Journal, 285
D

(2016) 698-708.
TE

[41] M. Baghayeri, A. Amiri, B. Maleki, Z. Alizadeh, O. Reiser, A simple approach for

simultaneous detection of cadmium (II) and lead (II) based on glutathione coated magnetic
EP

nanoparticles as a highly selective electrochemical probe, Sensors and Actuators B: Chemical,

273 (2018) 1442-1450.

C

[42] D. Qin, X. Hu, Y. Dong, X. Mamat, Y. Li, T. Wågberg, G. Hu, An electrochemical sensor
AC

based on green γ-AlOOH-carbonated bacterial cellulose hybrids for simultaneous determination

trace levels of Cd (II) and Pb (II) in drinking water, Journal of The Electrochemical Society, 165

(2018) B328-B334.

24
 ACCEPTED MANUSCRIPT

[43] L. Zhu, L. Xu, B. Huang, N. Jia, L. Tan, S. Yao, Simultaneous determination of Cd (II) and

Pb (II) using square wave anodic stripping voltammetry at a gold nanoparticle-graphene-cysteine

composite modified bismuth film electrode, Electrochimica Acta, 115 (2014) 471-477.

[44] G.-L. Wen, W. Zhao, X. Chen, J.-Q. Liu, Y. Wang, Y. Zhang, Z.-J. Huang, Y.-C. Wu, N-

PT
doped reduced graphene oxide/MnO2 nanocomposite for electrochemical detection of Hg2+ by

RI
square wave stripping voltammetry, Electrochimica Acta, 291 (2018) 95-102.

[45] L. Cui, J. Wu, H. Ju, Nitrogen-doped porous carbon derived from metal–organic gel for

SC
electrochemical analysis of heavy-metal ion, ACS Applied Materials & Interfaces, 6 (2014)

16210-16216.

U
[46] A. Afkhami, F. Soltani-Felehgari, T. Madrakian, H. Ghaedi, M. Rezaeivala, Fabrication and
AN
application of a new modified electrochemical sensor using nano-silica and a newly synthesized

Schiff base for simultaneous determination of Cd2+, Cu2+ and Hg2+ ions in water and some
M

foodstuff samples, Analytica Chimica Acta, 771 (2013) 21-30.

D

[47] H. Bagheri, A. Afkhami, H. Khoshsafar, M. Rezaei, A. Shirzadmehr, Simultaneous

TE

electrochemical determination of heavy metals using a triphenylphosphine/MWCNTs composite

carbon ionic liquid electrode, Sensors and Actuators B: Chemical, 186 (2013) 451-460.
EP

[48] G.L. Long, J.D. Winefordner, Limit of detection. A closer look at the IUPAC definition,

Analytical Chemistry, 55 (1983) 712A-724A.

C

[49] B. Cheng, L. Zhou, L. Lu, J. Liu, X. Dong, F. Xi, P. Chen, Simultaneous label-free and
AC

pretreatment-free detection of heavy metal ions in complex samples using electrodes decorated

with vertically ordered silica nanochannels, Sensors and Actuators B: Chemical, 259 (2018) 364-

371.

25
 ACCEPTED MANUSCRIPT

[50] X. Zhu, B. Liu, H. Hou, Z. Huang, K.M. Zeinu, L. Huang, X. Yuan, D. Guo, J. Hu, J. Yang,

Alkaline intercalation of Ti3C2 MXene for simultaneous electrochemical detection of Cd (II), Pb

(II), Cu (II) and Hg (II), Electrochimica Acta, 248 (2017) 46-57.

[51] S. Ashoka, P. Malingappa, Nano Zinc ferrite modified electrode as a novel electrochemical

PT
sensing platform in simultaneous measurement of trace level lead and cadmium, Journal of

RI
Environmental Chemical Engineering, (2018).

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

SC
trace Pb (II) and Cd (II) voltammetric determination, Analytica Chimica Acta, 769 (2013) 49-55.

[53] C.R.T. Tarley, V.S. Santos, B.E.L. Baêta, A.C. Pereira, L.T. Kubota, Simultaneous

U
determination of zinc, cadmium and lead in environmental water samples by potentiometric
AN
stripping analysis (PSA) using multiwalled carbon nanotube electrode, Journal of Hazardous

Materials, 169 (2009) 256-262.

M

[54] N. Promphet, P. Rattanarat, R. Rangkupan, O. Chailapakul, N. Rodthongkum, An

D

electrochemical sensor based on graphene/polyaniline/polystyrene nanoporous fibers modified

TE

electrode for simultaneous determination of lead and cadmium, Sensors and Actuators B:

Chemical, 207 (2015) 526-534.

EP

[55] N. Serrano, A. González-Calabuig, M. del Valle, Crown ether-modified electrodes for the

simultaneous stripping voltammetric determination of Cd (II), Pb (II) and Cu (II), Talanta, 138
C

(2015) 130-137.
AC

[56] Y. Yao, H. Wu, J. Ping, Simultaneous determination of Cd (II) and Pb (II) ions in honey and

milk samples using a single-walled carbon nanohorns modified screen-printed electrochemical

sensor, Food Chemistry, 274 (2019) 8-15.

26
 ACCEPTED MANUSCRIPT

[57] J. Yukird, P. Kongsittikul, J. Qin, O. Chailapakul, N. Rodthongkum, ZnO@graphene

nanocomposite modified electrode for sensitive and simultaneous detection of Cd (II) and Pb

(II), Synthetic Metals, 245 (2018) 251-259.

[58] X. Lin, Z. Lu, W. Dai, B. Liu, Y. Zhang, J. Li, J. Ye, Laser engraved nitrogen-doped

PT
graphene sensor for the simultaneous determination of Cd (II) and Pb (II), Journal of

RI
Electroanalytical Chemistry, 828 (2018) 41-49.

[59] R. Ouyang, Z. Zhu, C.E. Tatum, J.Q. Chambers, Z.-L. Xue, Simultaneous stripping

SC
detection of Zn (II), Cd (II) and Pb (II) using a bimetallic Hg–Bi/single-walled carbon nanotubes

composite electrode, Journal of Electroanalytical Chemistry, 656 (2011) 78-84.

U
[60] 28 - Copper, Silver and Gold, in: N.N. Greenwood, A. Earnshaw (Eds.) Chemistry of the
AN
Elements (Second Edition), Butterworth-Heinemann, Oxford, 1997, pp. 1173-1200.

[61] M. Sun, Z. Li, S. Wu, Y. Gu, Y. Li, Simultaneous detection of Pb2+, Cu2+ and Hg2+ by
M

differential pulse voltammetry at an indium tin oxide glass electrode modified by hydroxyapatite,
D

Electrochimica Acta, 283 (2018) 1223-1230.

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Table 1. Characteristics of calibration plots of the MGCE.

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Analytical parameter Pb(II) Cd(II)

Calibration equationa y=0.1541x+1.6868 y=0.1897x+3.7137

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R2 0.9988 0.9975
LCR (µg L-1) 0.4-120 0.2-140

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DL (ng L-1) 130 70
RSDb (%) 2.1 1.7

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a
y is in µA and x is in µg L-1.
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From eight determinations of 20 µg L-1 Pb(II) and Cd(II) mixed solution at same MGCE.
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Table 2. Comparison of analytical performance of various reported electrochemical sensors for measurement of lead and cadmium ions.

Electrodea Techniqueb LCR (µg L-1) DL (µg L-1) Sensitivityc (µA µg-1 L) Reference

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Pb(II) Cd(II) Pb(II) Cd(II) Pb(II) Cd(II)

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GSH-Fe3O4/GCE SWASV 0.5–100 0.5–100 0.182 0.171 0.1321 0.0748 [41]
VMSF/ITO DPV 5.2–8288.0 207.2–4144.0 0.5 25.8 - - [49]

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Alk-Ti3C2/GCE SWASV 20.7–310.8 11.2–168.6 8.5 11.0 0.1549 0.0636 [50]
ZnFe2O4/GCE DPASV 10–130 10–130 0.56 1.26 0.1753 0.1335 [51]

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Bi-xerogel/GCE ASV 1.04–20.72 0.56–11.24 1.3 0.37 1.35 3.0 [52]

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MWCNTs/CPE PSA 58.4–646.2 58.4–646.2 6.6 8.4 - - [53]
Gr-PANI-PS/SPCE SWASV 10–500 10–500 3.30 4.43 0.9351 0.9214 [54]

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CB-18-crown-6/GCE DPASV 5.0–186.5 7.9–191.1 1.5 2.4 0.021 0.016 [55]
SWCNHs/SPE SWASV 1.0–60.0 1.0–60.0 0.4 0.2 0.300 0.201 [56]

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ZnO-Gr/SPCE ASV 10–200 10–200 0.8 0.6 0.2803 0.2941 [57]

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N@LEG/GCE DPASV 0.5–380 5–380 0.16 1.08 0.13 0.04 [58]
Hg-Bi-SWNTs/GCE ASV 0.5–130 0.5–130 0.18 0.076 1.15 0.41 [59]
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g-C3N4/SPE SWASV 30–110 30–120 10.4 21.8 0.0169 0.0443 [60]
GO-Fe3O4-PAMAM/GCE SWASV 0.4–120 0.2–140 0.13 0.07 0.1541 0.1897 This work
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a
GSH-Fe3O4: Glutathione functionalized iron oxide nanocomposite, GCE: Glassy carbon electrode, VMSF: Vertically-ordered mesoporous silica film, ITO: Indium tin oxide, Alk-Ti3C2: Alkalization-
intercalated Ti3C2, ZnFe2O4: Nano sized zinc ferrite particles, Bi-xerogel: Bismuth-dispersed xerogel, MWCNTs: Multiwalled carbon nanotubes, Gr-PANI-PS: Graphene-polyaniline-polystyrene
nanoporous fibers, SPCE: screen-printed carbon electrode, CB-18-crown-6: 4-carboxybenzo-18-crown-6, SWCNHs: Single-walled carbon nanohorns, SPE: Screen-printed electrode, ZnO-Gr: Zinc
oxide-graphene nanocomposite, N@LEG: Nitrogendoped laser engraved graphene, SWNTs: Single-walled carbon nanotubes, g-C3N4: Graphitic carbon nitride, SPE: screen-printed electrode, GO-
Fe3O4-PAMAM : Poly(amidoamine) dendrimer functionalized magnetic graphene oxide.
b
SWASV: Square wave anodic stripping voltammetry, DPV: Differential pulse voltammetry, DPASV: Differential pulse anodic stripping voltammetry, ASV: Anodic stripping voltammetry, PSA:
Potentiometric stripping analysis.
c
Based on calibration curve slope.
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Figure Legends

Scheme 1. Representation route for preparation of GO-Fe3O4-PAMAM nanocomposite.

Figure 1. SEM images of GO (A), GO-Fe3O4 (B) and GO-Fe3O4-PAMAM (C).

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Figure 2. SWASVs of bare GCE, GO/GCE, GO-Fe3O4/GCE, GO-PAMAM/GCE and GO-

Fe3O4-PAMAM/GCE in the presence of 20 µg L-1 Cd(II) and 20 µg L-1 Pb(II). Other

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conditions: pH=4.5, accumulation medium=0.1 mol L-1 HAc-NaAc+ 0.1 mol L-1 KCl,

mL-1,

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nanocomposite concentration=1.0 mg accumulation potential=-1.1 V,

accumulation time=160 s, pulse amplitude=25 mV, frequency=15 Hz and potential

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step=4 mV.
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Figure 3. Anodic peak currents obtained by SWASV as function of pH (A), GO-Fe3O4-PAMAM

concentration (B), accumulation potential (C) and accumulation time (D) at the
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proposed MGCE. Other conditions were the same as in Fig. 3. Data are depicted as

mean ± SD (error bar) of triplicate experiments.

D

Figure 4. SWASVs of MGCE in the solutions with different concentrations (bottom to top: 0.2,
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1.0, 5.0, 10.0, 20.0, 35.0, 55.0, 80.0, 100.0, 120.0, 140.0 µg L-1) of cadmium ions in

the presence of 20 µg L-1 lead ions (A). SWASVs of MGCE in the solutions with
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different concentrations (bottom to top: 0.4, 1.0, 5.0, 10.0, 20.0, 35.0, 55.0, 80.0,
C

100.0, 120.0 µg L-1) of lead ions in the presence of 20 µg L-1 cadmium ions (B). The
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insets show calibration plots of the stripping peak currents vs. the Cd(II) and Pb(II)

concentrations. Other conditions were the same as in Fig. 3.

Figure 5. Simultaneous determination of Cd(II) and Pb(II) at different concentrations. The inset

shows calibration plots in optimum conditions at MGCE.

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Highlights

Simultaneous determinations of Cd(II) and Pb(II) in water matrix by GO-Fe3O4-

PAMAM/GCE were investigated.

Dendritic macromolecule is applied as a chelating agent in stripping analysis of heavy

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metals.

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The proposed sensor presents well-defined stripping peaks and broad linear ranges.

The application of the modified electrode for real sample analysis was also demonstrated.

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