Sensors and Actuators B 210 (2015) 113119

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Sensors and Actuators B: Chemical

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

Submonolayer deposition on glassy carbon electrode for anodic

stripping voltammetry: An ultra sensitive method for antimony
in tap water
Huaifang Fang a,b,,1 , Jie Zhang a,1 , Shu Zhou a , Wei Dai a , Chunya Li a ,
Dongyun Du a , Xinyu Shen b
a
Key Laboratory of Analytical Chemistry of the State Ethnic Affairs Commission, College of Chemistry and Materials Science,
South-Central University for Nationalities, Wuhan 430074, China
b
Key Laboratory of Analytical Chemistry for Biology and Medicine, Wuhan University, Ministry of Education, 430072, China

a r t i c l e i n f o a b s t r a c t

Article history: Atomic layers of antimony were electrodeposited onto glassy carbon electrode in overpotential region.
Received 29 June 2014 The antimony deposition was characterized by chronocoulometry and scanning electron microscopy.
Received in revised form Based on the excellent electrochemical properties of the glassy carbon/antimony system, a simple method
12 December 2014
was developed for rapid and reliable determination of ultra-trace Sb(V) by square-wave anodic stripping
Accepted 19 December 2014
voltammetry. The key operational parameters of inuencing the electroanalytical response of Sb, such as
Available online 27 December 2014
deposition potential, deposition time, and composition of the measurement solution, were investigated.
Under the optimized condition, the method provided a linear calibration ranging from 1 to 16 pg L1
Keywords:
Monolayer deposition
with a respective correlation coefcient of 0.9906. The detection limit was 1.64 fmol L1 , which is the
Anodic stripping voltammetry lowest ever reported for an electroanalytical technique and one of the lowest analytical methods for
Ultra sensitive Sb(V) determination. The relative standard deviation for a Sb(V) solution (5 pg L1 ) was 3.2% for eight
Antimony successive assays. Finally, the method was applied to the determination of antimony in tap water and
compared with inductively coupled plasma mass spectrometry technique.
2014 Elsevier B.V. All rights reserved.

1. Introduction antimony present in surface water are antimonate (Sb(OH)6 ) and

Antimony (Sb) is a metalloid element that occurs naturally due
to rock weathering, soil run-off and atmospheric deposition in the
environment. However, its presence in the environment is also
caused by various anthropogenic activities. Industrially, antimony
is used in the fabrication of lead alloys, re retardants, glassy and
ceramics, batteries and polyethylene terephthalate as a polycon-
densation catalyst [1,2]. Normal concentrations of antimony in
water sources vary from a few ng L1 to a few mg L1 , depend-
ing on localization and/or anthropogenic activity. Typical levels in
rivers and lakes are <8 nM (1 ppb) but can be as low as 0.2 ng L1 in
pristine ground waters [1,3]. The two common inorganic forms of
Corresponding author at: Key Laboratory of Analytical Chemistry of the State
Ethnic Affairs Commission, College of Chemistry and Materials Science, South-
Central University for Nationalities, Wuhan 430074, China. Tel.: +86 135 17295825;
fax: +86 27 67842752.
E-mail address: hffang@mail.scuec.edu.cn (H. Fang).
1
These authors contributed equally to this work.
antimonite (Sb(OH)3 ). The inorganic oxidized Sb(V) species are pre-
dominant in oxic waters (with 7094% of the total antimony being
present as Sb(V) species), the reduced Sb(III) species occurring at
much lower levels due to biotic and abiotic reduction processes
coupled with slow oxidation kinetics [4].
The ecotoxicity of antimony is considered poisonous to humans
and animals at high dosage with marked similarities to the toxic
nature of arsenic [5]. Antimony and its compounds are listed as
pollutants of priority interest by the United States Environmental
Protection Agency and the Council of the European Communities,
which have considered a maximum contaminant level of antimony
in drinking water of 56 g L1 [6,7]. Therefore, developing sensi-
tive and selective methods for the determination of antimony in
various samples is of great importance.
The determination of antimony in various sample matrices
can be performed by microwave induced plasma-atomic emission
spectrometry [8], inductively coupled plasma mass spectrome-
try [9], solvent extraction-atomic absorption spectrometry [10],
laser induced uorescence [11] and high performance liquid chro-
matography [12]. However, the sensitivity of these methods is

http://dx.doi.org/10.1016/j.snb.2014.12.093
0925-4005/ 2014 Elsevier B.V. All rights reserved.
114 H. Fang et al. / Sensors and Actuators B 210 (2015) 113119
sometimes inadequate to determine ppt or sub-ppt concentra-
tion of Sb in environmental samples. Preconcentration is required,
which is time consuming, laborious and may cause contamination.
Moreover, these techniques are impractical for on-site screening
owing to their size and analytical costs. In this aspect, advanced
electroanalytical methods provide a favorable alternative offering
sensitive and selective measurements associated with relatively
simple, portable and non-expensive instrumentation [13].
Stripping voltammetry/chronopotentiometry has been recog-
nized as one of the most convenient choices for measuring trace
metal ions. Due to the unique capability of pre-concentrating ana-
lytes at/in the working electrode surface, electrochemical stripping
analysis allows quantication of, e.g. toxic metal ions down to low
microgram per liter or even nanogram per liter concentration levels
[14]. Performance of a stripping voltammetric procedure depends
primarily on the appropriate choice of the working electrode. Many
electrodes, such as, the mercury drop [1519], mercury lms [20],
solid gold [2124], gold lms [25], bismuth lms [2628], anti-
mony lms [29,30], gold nanoparticles [31], or silver nanoparticles
[32], carbon material electrodes [3335], have been developed.
Among them, mercury-based electrodes have been most widely
used in the past six decades due to superior electroanalytical per-
formance of mercury, despite of its well-known toxic character and
difculties associated with its handling, storage, and disposal. Car-
bon materials and bismuth are two most popular materials for
electrochemical stripping analysis in recent years. In particular,
glassy carbon electrode (GCE) has gained wide acceptance due to
its chemical inertness, low sensitivity to memory effects and easy
modication.
It has been reported antimony(III) is more toxic than the pen-
tavalent species [36]. However both species are generally found
in environmental samples at varying ratios and as such guidelines
regarding maximum contaminations consider the total antimony
concentration. Electrochemical methods for the determination of
total antimony have mostly focused on the detection of Sb(III)
because of the perceived electro-inactivity of Sb(V). Prior to
research based on depositing beyond the hydrogen wave [24,34],
stripping voltammetry to determine Sb(V) requires harsh acidic
media or pre-reducing agents to convert all Sb(V) to Sb(III) within
the sample solution prior to analysis [28,35,37,38]. The reduction
step is time-consuming, might be difcult to implement, and also is
a major potential source of contamination at low antimony levels.
The high acidic conditions are not appealing for routine use. Up to
now, the most sensitive method for Sb(V) detection was achieved
by anodic stripping voltammetry on a vibrating gold microwire,
with a detection limit of 5 pM after 60 s accumulation time [24].
Underpotential deposition (UPD) is the electrochemical deposi-
tion of foreign metals onto substrates at potentials positive relative
to the reversible Nernst potential for bulk deposition. During the
deposition step, the adatom coverage of trace elements is in the
range of 0.011% and no bulk deposition is invoked for metals
that exhibit UPD [39]. Because UPD is a monolayer phenomenon,
the stripping peak of the monolayer usually shows more sharp
and reproducible characteristics [40]. UPD was usually achieved
with metal electrode, such as Au, Pt, Ag and other materials [39].
To the best of authors knowledge, the experiment of monolayer
deposition on unmodied glassy carbon electrode has never been
reported.
In the present work, ultra-trace Sb(V) (from 1 to 50 pg L1 ) was
deposited on a glassy carbon electrode in non-deaerated acetate
buffer. Then, square-wave anodic stripping voltammetry (SW-ASV)
was applied to stripping monolayer of Sb on the electrode. The fac-
tors that inuence the sensitivity of detection, such as pH of buffer,
deposition potential and accumulation time, were optimized. In
addition, the interferences from foreign ions were examined. Fur-
thermore, the new protocol was also tested via measurement of
ultra-trace antimony in tap water and compared with the ICP-MS
technique.
2. Materials and methods
2.1. Reagents and materials
All chemicals employed in this work were of analytical reagent
grade unless stated otherwise. Throughout the experimental work,
all solutions were prepared from doubly deionized water obtained
by passing through a Milli-Q Millipore laboratory water purica-
tion system (Millipore, Bedford, USA). All the experiments were
carried out at room temperature (approximately 25 C) and without
removing oxygen. Stock standard solutions of Sb(V) were prepared
by dissolving appropriate amounts of potassium hexahydroxy anti-
monite(V) (Fluka) in hot water. Stock Sb(III) solution was obtained
by dissolving potassium antimony tartrate(III) (Aladdin Reagent
Co., Shanghai, China) in ethanol. The sample was obtained by
diluting the stock standard sample with supporting electrolyte to
the desired concentration in 10 mL polyethylene centrifuge tube.
Flasks containing Sb(III) standards solutions were wrapped in alu-
minum foil paper to avoid oxidation. Metal solutions (CuSO4 5H2 O,
MgCl2 6H2 O, Al(NO3 )3 , Cr(NO3 )3 9H2 O, Cd(NO3 )2 and Bi(NO3 )3 )
(Sinopharm Chemical Reagent Co. Ltd., Shanghai, China) were used
for interference experiments; HNO3 , CH3 COOH (Sinopharm Chem-
ical Reagent Co. Ltd., Shanghai, China) was analytical reagent grade
and used as received; sodium acetate (purity 99.99%) was from
Aladdin (Aladdin Reagent Co., Shanghai, China).
2.2. Equipment
Cyclic voltammetry, chronocoulometry and SW-ASV were
performed with a CHI-660D electrochemical station (Chenhua
Instruments Co., Shanghai, China), in connection with a per-
sonal computer. Scanning electron microscopy (SEM) images were
obtained using a quanta 200 scanning electron microscopy (FEI,
Holland). The MS-H-S meter (Dragon Instrumentation Co. Ltd.,
China) was used to measure the pH of solution. A conventional
three-electrode system consisted of a glassy carbon electrode as
the working electrode with a diameter of 3.0 mm, a counter elec-
trode made of platinum wire, and an Ag/AgCl/3 M KCl reference
electrode. All electrochemical measurements were carried out in a
20 mL quartz electrochemical cell in a Faraday cage. All potentials
were given with respect to the Ag/AgCl electrode. In chronocoulom-
etry and anodic stripping measurements, a Teon-coated magnetic
stirring bar (approximately 300 rpm) was employed during the
electrochemical deposition step. The electrodes were stored in air
or Milli-Q water. All glassware, polypropylene sample cups and
polyethylene bottles, was carefully cleaned by soaking in (1 + 1)
nitric acid over 24 h, followed by thorough rinsing with copious
amounts of ultrapure water, to avoid accidental contamination.
2.3. Measurement procedure
The bare glassy carbon electrode was polished to a mirror using
0.3 and 0.05 m Al2 O3 powder, successively, and rinsed thoroughly
with doubly distilled water between each polishing step. Then it
was washed successively with 1:1 (v/v) HNO3 aqueous solution,
doubly distilled water, ethanol and doubly distilled water in ultra-
sonic bath and dried in air. 0.1 M acetate buffer (pH 4.0) was used as
the supporting electrolyte except a part of the optimization exper-
iments.
The established procedures for the determination of
Sb(V)/Sb(III) by SW-ASV were carried out as follows: 10 mL
of acetate buffer solution (0.1 mol L1 ) was pipetted into the
quartz electrochemical cell and antimony from a stock solution
 H. Fang et al. / Sensors and Actuators B 210 (2015) 113119
4.5
4.0
3.5
3.0
Peak current ( A)
2.5
2.0
1.5
1.0
0.5
0.0
3.0 3.5 4.0 4.5 5.0 5.5
pH of buffer
Fig. 1. Effect of the pH value of the measure solution on the peak current of 20 pg L1
Sb(V) at the GCE. Solution: 0. 1 M sodium acetate. Deposition potential: 0.9 V (vs.
Ag/AgCl); deposition time: 240.0 s; quiet time: 10.0 s; frequency: 20.0 Hz; pulse
amplitude: 25.0 mV; scan increment: 4.0 mV. All measurements were made in trip-
licate and the results averaged.
was added to the cell to obtain the accurate concentration under
investigation. Accumulation was carried out at a given deposition
potential for a xed time at a stirring speed of 300 rpm. After an
equilibration time of 10 s, the voltammogram was recorded by
applying a positive-going SW-ASV potential scan from 1.0 to
0.4 V with a frequency of 20.0 Hz, pulse amplitude of 25.0 mV, and
scan increment of 4.0 mV. After the measurement, a 60 s clean step
at 1 V under stirring was used to remove the residual antimony.
No deaeration of measurement solutions was applied in any of
SW-ASV experiments.
2.4. Voltammetric determination of Sb(V) in natural waters
Antimony(V) in tap water samples (collected from the lab water
pipeline) was determined by SW-ASV as described above. An
aliquot of sample solution (1.0 mL) was introduced into 9.0 mL of
acetate buffer solution (0.111 mol L1 , pH 4.0). To eliminate matrix
effects, all water samples were analyzed by standard addition
method. Appropriate standard solutions of analytes were added
three times in order to calculate the concentration of metal ions in
water sample. For evaluation measurements, an ICP-MS unit model
NexIon300X (PerkinElmer, California, USA) was used.
3. Results and discussion
3.1. Optimum experimental conditions
The Sb(V) is often considered to be electroinactive, however
its electrochemical reduction was observed in high acidic chloride
containing solution (5 M HCl) [37,38]. By taking deposition poten-
tial (1.8 V) far more negative than the hydrogen wave, deposition
and stripping of Sb(V) can be realized in mildly acidic conditions
(pH 2) [34]. As dissolved Sb(V) is present primarily as the anionic
species Sb(OH)6 at pH 3, less acidic electrolytes are more favor-
able. Moreover, comparing with harsh acidic buffer used, hydrogen
evolution is reduced in mildly acidic conditions, which gave a much
wider potential window. In our experiment, the acetate solution,
which is a more mildly acidic buffer, was adopted as supporting
electrolytes. The electrochemical reduction of Sb(V) at the GCE
was investigated using SW-ASV mode in the pH range of 3.05.5
as depicted in Fig. 1. The electrode response increased as the pH
decreased from 5.5 to 3.0. However, the split peaks were observed
115
sometimes when pH was below 4.0. Thus, an acetate solution with
pH 4 was chosen for further work.
The effect of deposition potential on the peak current of
20 pg L1 Sb(V) was studied in the potential range from 0.3 to
1.1 V with 240 s of accumulation. As can be seen from Fig. 2(a), in
the range of potential from 0.3 to 0.9 V, peak currents of anti-
mony increased remarkably with decreasing deposition potential.
The stripping signal increased slightly when deposition potentials
were or below 1.0 V. At 1.0 V, the production of hydrogen gas
was high enough so that small gas bubbles could be observed on
the electrode surface. Moreover, the use of more negative electrol-
ysis potential can cause problems with the SW-ASV determination
of antimony, owing to the tendency to codeposit other metal ions,
such as copper and lead. Considering the above mentioned obser-
vations, we selected the value of 0.9 V as the optimum deposition
potential.
One of the interesting things was the peak heights of anti-
mony were 2.80 107 A for a deposition potential of 0.3 V, as the
potential was not sufciently negative to initiate reduction of the
Sb(V) to the antimony. A possible reason for the observed behav-
ior can be as follows: the Sb(V) groups adsorb onto hydroxide or
oxide mineral surfaces of the glassy carbon electrode and/reduced
to certain form of Sb(III) during deposition, which is further reduced
to antimony and oxidized to Sb(III) in the anodic stripping scan
(from 1.0 to 0.4 V). A similar result has been observed by Martnez
and coworker while determining Sb(V) by adsorptive stripping vol-
tammetry using pyrogallol [15]. The reduction potentials of 0.3 V
was not sufciently negative to initiate reduction of most metal
cations, which allowed us to determine trace Sb(V) in the present
of high amount of interference metal ions. This attractive charac-
teristic would be application-specic. The other meaningful thing
was a broad peak at approximately 0.60 V appeared in the anodic
stripping scan when the deposition potential was or below 0.7 V.
The peak height increased with decreasing deposition potential.
This should be a oxidation peak of the oxidable antimony species
adsorbed on glassy carbon electrode surface as the peak height is
proportionate to the concentration of Sb(V). Further experiment is
needed to conrm the component.
The effect of deposition time on the stripping performance for
20 pg L1 of Sb(V) was investigated in the range from 60 to 360 s
as depicted in Fig. 2(B). The stripping signal for Sb(V) increased
almost linearly up to 360 s. This indicates that no saturation of elec-
trode surface was observed within this time interval. This pattern
undoubtedly allows operators to use correspondingly prolonged
deposition time to achieve a higher sensitivity. Up to 240 s, the
peak of antimony was sharp and the height increased linearly; fur-
ther prolongation of the accumulation time gave higher but broader
peaks. Hence, an accumulation time of 240 s was used in all subse-
quent measurements.
In order to understand the electrochemical behavior of anti-
mony, we studied the reduction/oxidation (deposition/dissolution)
pattern of the antimony lm on a glassy carbon substrate elec-
trode. As can be seen from Fig. 3, for Sb(V) at 50 pg L1 , the
peak current at 0.164 V increased linearly with the accumu-
lation time from 60 to 180 s with a deposition at 0.9 V. A
small peak at 0.196 V (0.331 A) was seen for 120 s deposi-
tion, and increased to 2.379 A for 180 s accumulation (for Sb(V)
at 0.164 V: ip (A) = 0.02301t 0.7381, R2 = 0.9972; for Sb(V) at
0.196 V: ip (A) = 0.03413t 3.6694, R2 = 0.9880). The difference of
oxidation potential implies the elemental antimony oxidized under
difference condition. As previously reported, the peak potential
shifts toward less or more negative potentials when attractive or
repulsive forces are operative, respectively [41]. The glassy carbon
electrodes, pre-treated at 1 V for 30 s in acidic buffer, have increased
oxygen functionalities, especially quinones, on the electrode sur-
face. These carbonoxygen functionalities provide an electrostatic
116 H. Fang et al. / Sensors and Actuators B 210 (2015) 113119

(a) 3.0 (b) 5.5

5.0
4.5
2.5
4.0

Peak current (A)

Peak current (A)

3.5
2.0
3.0

1.5 2.5
2.0
1.0
1.5
1.0
0.5
0.5

0.0 0.0
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 100 150 200 250 300 350 400
Deposition potential (V) Deposition time (s)

Fig. 2. Effect of deposition potential (a) and deposition time (b) upon the anodic stripping voltammetric response of Sb(V) in 0.1 mol L1 acetate buffer (pH 4) at a GCE. In (A)
deposition for 240 s, in (B) deposition at 0.9 V. All Other conditions are as in Fig. 1.

60 s of antimony on the electrode was calculated by Faradays laws of

90 s electrolysis (Eq. (2)):
-1
120 s
150 s n = (Q/F)(1/z) (2)
-2 180 s
With n is the amount of substance liberated, Q is the total elec-
tric charge passed through the substance, F is the Faraday constant
-3
(F = 96485 C mol1 ), z is the valency number of ions of the substance
Current ( A)

(electrons transferred per ion). The surface coverage of antimony

-4
-5
-6
-7
-0.8 -0.6 -0.4 -0.2
Potential (V)
Fig. 3. Comparison of anodic stripping voltammetric responses for 50 pg L1 Sb(V)
on GCE with varying accumulation time. The inset depicts the corresponding cali-
bration plot of signal at 0.196 and 0.164 V, respectively. Solution: 0.1 M acetate
solution (pH 4). Deposition potential: 0.9 V (vs. Ag/AgCl); quiet time: 10.0 s; fre-
quency: 20.0 Hz; pulse amplitude: 25.0 mV; scan increment: 4.0 mV.
attraction of the accumulated elemental antimony to the substrate
surface, which contribute to a more positive oxidation potential
needed for partial antimony monolayer.
Further experiment was taken to quantize the amount of ele-
mental antimony deposited on GCE. The real surface area of GCE
was calculated by tting the cyclic voltammetry current obtained
in a stagnant solution of 0.1 M KCl + 5 mM K3 Fe(CN)6 according to
the RandlesSevick equation (Eq. (1)). The surface area of GCE is
0.054 cm2 :
ip = 268600n3/2 AD1/2 C v1/2
With ip is current maximum in amps, n is the number of
exchanged electrons (n = 1), A is electrode area in cm2 , D is the diffu-
sion coefcient of Fe(CN)6 3 in 0.5 M KCl (D = 7.17 106 cm2 s1 ),
C is Fe(CN)6 3 bulk concentration (mol cm3 ) and v is the scan rate
in V/s.
Then we performed chronocoulometry measurements in a
model 50 pg L1 Sb(V) in 0.1 mol L1 acetate buffer after pre-
deposition, under the condition used in the SW-ASV. The amount
on GCE was 2.63 1011 mol cm2 , which indicated that metallic
deposits covered very low portion of the GCE surface. This was
conrmed by SEM imaging (Fig. 4). As shown in Fig. 4(a), the unmo-
died glassy carbon electrode surface is very at. Fig. 4(b) shows
the surface of a glassy carbon electrode prepared by electrodeposi-
tion with 50 pg L1 Sb(V). The surface is sparsely covered with a few
akes, which should be antimony deposits. The presence of anti-
mony deposits is more clearly from the inset picture of Fig. 4(b). As
0.0 0.2 the structure of the electrode surface remains mainly unchanged, it
is not necessary for time-consuming mechanical treatment of the
electrode surface between series of experiments.
3.2. Calibration, detection limit and precision
To evaluate the electroanalytical performance of SW-ASV, some
parameters, such as linearity, limit of detection, and reproducibil-
ity, were determined under the optimized conditions. We rstly
obtained the standard curve by increasing the concentrations
of analyte step by step based on the optimized conditions. As
can be seen from Fig. 5, the GCE revealed good linear behavior
for Sb(V) at potential of 0.196 V, in the examined concentra-
tion range from 1 to 16.0 pg L1 . The regression equation was
ip(Sb(V)) (A) = 0.7675 + 0.09159CSb(V) (pg L1 ) with a R2 value of
0.9906. RSD were 3.2% for 5 pg L1 Sb(V) with eight repetitive mea-
surements. Under the optimized conditions, the detection limit was
0.2 pg L1 (1.64 fmol L1 ). The detection limit (DL) was calculated
as DL = kSB /b (where k is a constant equal to 3, as recommended by
IUPAC; SB is the standard deviation of the blank signal, with current
(1) values measured at the same potential as for the antimony signal;
and b is the slope of the calibration plot). To the best of our knowl-
edge, this is the lowest DLs ever reported for an electroanalytical
method and at least 3000 times lower than previously reported
methods with direct reduction of Sb(V) (Table 1). The calibrations
performed have revealed a slightly shift of the response toward
less positive potentials. As previously reported, the peak potential
shifted toward more negative potentials as metal analyte concen-
tration increasing [41]. Finally, the high sensitivity of monolayer
deposition is not restricted to the antimony on GCE. Rather, it can
 H. Fang et al. / Sensors and Actuators B 210 (2015) 113119 117

Table 1
Comparison of this method for the determination of Sb(V) with other electrochemical techniques using different electrodes.

Technique Electrode Modication/chelator Detection limit (M) References

Mercury electrodes
DP ASV HMDE 5.00E08 [17]
DP ASV HMDE 9.00E11 [38]
LS ADCSV HMDE Catechol 2.00E10 [42]
DP ADCSV HMDE Chloranilic acid 4.60E09 [18]
DP ADCSV HMDE Pyragallol red 4.87E08 [16]
DP ADCSV HMDE Pyragallol 2.30E08 [19]
DP ADCSV HMDE Pyragallol 9.48E09 [15]
Metal electrodes
PSA Gold tube 2.63E09 [23]
DP ASV Gold microwire 5.00E12 [24]
Carbon electrodes
SQW CSV EPPG Bismuth 1.64E11 [27]
SQW ASV EPPG Bismuth 4.11E11 [28]
PSA MW-CNPE 5.09E08 [35]
DP ASV EPPG 5.80E09 [34]
SW-ASV GC 1.64E15 This work

DP: differential pulse, ASV: anodic stripping voltammetry, CSV: cathodic stripping voltammetry, LS: linear sweep, MW-CNPE: multiwall carbon nanotube paste electrode,
PSA: potentiometric stripping analysis, SQW: square wave, AdCSV: adsorptive cathodic stripping voltammetry.

-1.0

-1.5

-2.0

-2.5
Current (A)

-3.0
1 pg/L
3 pg/L
-3.5 5 pg/L
8 pg/L
11pg/L
-4.0
13pg/L
16pg/L
-4.5

-0.8 -0.6 -0.4 -0.2 0.0 0.2

Potential (V)

Fig. 5. SW-ASV of Sb(V) with different concentrations (from 1 to 16 pg L1 ). The

inset depicts the corresponding calibration plot. Deposition potential: 0.9 V (vs.
Ag/AgCl); deposition time: 240 s; other experimental conditions are as in Fig. 3.

be applied to any anodic stripping process where the analyte is elec-

trochemically deposited onto a suitable substrate surface, forming
a lm (in an ideal case a monolayer). We also realized sub-ppt con-
centration of tin determination with similar method and the results
will be reported separately.

4. Interference study

Possible interference of other ions in the SW-ASV determination

of Sb(V) was studied by adding the investigated ions to a solution of
0.1 ng L1 Sb(V), under the optimized conditions. Interfering ions

Table 2
Tolerance limits of foreign ions in the determination of Sb(V) (0.1 ng L1 ). All mea-
surements were made in triplicate and the results averaged.
Fig. 4. Scanning electron microscope images of unmodied glassy carbon electrode
(a) and Sb nanoparticle-modied glassy carbon electrode prepared by electrodepo- Element Tolerance limit (ng L1 ) Ion:Sb ration
sition. (b) Films were electroplated at a potential of 0.90 V for 240 s from a pH 4
+ +
acetate solution containing 50 pg L1 Sb(V), with stirring. K , Na 500 5000
Cd2+ , Mg2+ , Al3+ , Cu2+ 100 1000
Bi3+ , Cr3+ 1 10
118 H. Fang et al. / Sensors and Actuators B 210 (2015) 113119

Table 3
Peak current at 0.6 V for antimony(V) with and without interferences. All measurements were made in triplicate and the results averaged.

Concentration of Sb(V) (pg L1 ) 1 3 5 7 9 11 13

Current without adding (A) 0.592 0.683 0.741 0.757 0.895 0.951 1.024
Current in the presence of 20 pg L1 Cr3+ (A) 0.588 0.675 0.743 0.761 0.881 0.944 1.031

Table 4 10 times dilued water

Current values obtained for the determination of known concentrations of anti- diluted water+5 pg/L
mony(III) and antimony(V) using the proposed method. All measurements were -2.0 diluted water+10 pg/L
made in triplicate and the results averaged. diluted water+15 pg/L
-2.5
Compound Concentration (pg L1 ) Current (A)

Potassium hexahydroxy antimonite 1 0.85 0.05 -3.0

Potassium antimony tartrate 1 0.84 0.08
Antimonous chloride 1 0.48 0.02 -3.5

Current ( A)
-4.0

were added at different concentrations (max. 5000 fold) higher

than the concentration of Sb(V) until they produced a change of
5% in height of initial peak current. The results are summarized in
Table 2. It can be seen that the following ions, like, K+ , Na+ , Mg2+ ,
Cd2+ , Cu2+ and Al3+ had little interference for the detection. Some
metal ions, such as Cr3+ , and Bi3+ , had a serious interference. How-
ever, it is important to note that the second peak of Sb(V) at more
negative potential (at 0.60 V) remained practically unaffected in
the presence of all afore mentioned heavy metals, and can thus be
favorably exploited for antimony assessment in those cases, when
the rst peak of antimony is seriously obscured by, e.g. Bi3+ [33].
Table 3 shows peak current at 0.6 V in absence of interferences and
in the present of 20 pg L1 Cr3+ . The signal of Sb(V) was similar in the
absence and presence of 20 pg L1 Cr3+ . As can be seen from Table 3,
the peak current increase slowly with the concentration of Sb(V).
The regression equation was ip (Sb(V)) (A) = 0.5543 + 0.0354CSb (V)
(pg L1 ) with a R2 value of 0.984.
The same responses were obtained for potassium antimony tar-
trate and potassium hexahydroxy antimonite; however, the signal
for antimonous chloride was only half of them (Table 4). The rea-
son maybe as fellow: the glassy carbon electrodes, pre-treated at
1 V for 30 s in acidic buffer, have increased oxygen functionalities on
the electrode surface. These carbonoxygen functionalities linked
with the antimonite (Sb(OH)6 ) or antimony tartrate by hydro-
gen bonds, which accumulate antimony species during deposition
and prevent antimony species come off from the electrode sur-
face before the redissolution step. However, antimonous chloride
cannot interact with the electrode surface, which may lose part of
antimony species under stirring condition.
4.1. Analytical application to tap water sample
The method was applied to the analysis of antimony in tap water
sample which was collected from our laboratory. As the amount
of antimony in tap water reported is beyond the linear range of
our method, the water sample was diluted 10 times before it was
electrochemically analyzed. The concentration of Pb2+ , Cd2+ , Zn2+
and Cu2+ in tap waters is at least 100 times higher than that of Sb.
In order to eliminate the matrix effect, the protocol comprised a
standard addition method with three consecutive standard addi-
tions of 5 pg L1 Sb(V). As depicted in Fig. 6, an linear dependence
was achieved with a correlation coefcient R2 of 0.9948 and the
corresponding concentration of Sb(V) was evaluated by extrapola-
tion revealing a value of 37.4 pg L1 . Then the actual concentration
should be 374 pg L1 . The ICP-MS yielded a concentration of anti-
mony equal to 450 70 pg L1 . Major discrepancy can be due to
certain non-reducible (maybe insoluble) antimony species under
deposition potential of 0.9 V while the ICP-MS detect the total
antimony present in tap water.
-4.5
-5.0
-5.5
-0.8 -0.6 -0.4 -0.2 0.0 0.2
Potential (V)
Fig. 6. SWASV of tap water sample and after three standard additions (aliquots
of 5 pg L1 ) obtained at the GCE. Tap water was diluted 10 times with doubly dis-
tilled water. The inset shows the corresponding standard plot. Deposition potential:
0.9 V (vs. Ag/AgCl); other conditions are as in Fig. 3.
5. Conclusions
We have reported a novel method that determines sub-ppt con-
centration of Sb(V) using an unmodied glassy carbon electrode
in the presence of dissolved oxygen under mildly conditions. It
has a variety of merits such as the following: (1) submonolayer
deposition of antimony on GCE was obtained, which is the rst
report of monolayer deposition on carbon material electrodes; (2)
the detection was performed in pH 4 acetate buffer using unmodi-
ed GCE electrodes with a deposition potential of 0.9 V. Neither
harsh acidic solution nor chemical reducing agents were necessary.
Moreover, more positive deposition potential effectively avoids
the formation of hydrogen bubbles and codeposition with other
metals during the deposition; these attractive characteristic would
be application-specic; (3) detection limit for Sb (V) is the lowest
reported for an electroanalytical method; It also compares favor-
ably with most spectroscopic and ICP-MS techniques while being a
relatively cheap and simple method to implement. Moreover, the
high sensitivity of monolayer deposition is not restricted to the
antimony on GCE.
Author contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the nal version of the
manuscript.
Conict of interest
The authors declare no competing nancial interest.
Acknowledgements
The authors gratefully acknowledge the nancial supports from
Natural Science Foundation of China (Nos. 21275165, 21275166),
Key Laboratory of Analytical Chemistry for Biology and Medicine
 H. Fang et al. / Sensors and Actuators B 210 (2015) 113119
(Ministry of Education) (No. ACBM2012005), the Natural Science
Foundation of South-Central University for Nationalities (Nos.
CZY12020, YCZY12020, MZY13006), Heavy Metal Engineering Cen-
ter of Wuhan City (No. 201160638171).
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Biographies
Huaifang Fang is associate professor in the College of Chemistry and Materials Sci-
ence, South-Central University for Nationalities. His current interests are separation
science, ionic liquid and electrochemical sensors.
Jie Zhang is an undergraduate student in the College of Chemistry and Materials
Science, South-Central University for Nationalities. Her current interests are elec-
trochemical sensors.
Shu Zhou is a graduate student in the College of Chemistry and Materials Science,
South-Central University for Nationalities. Her current interests are electrochemical
and uorescent sensors.
Wei Dai is an undergraduate student in the College of Chemistry and Materials
Science, South-Central University for Nationalities. Her current interests are elec-
trochemical sensors.
Chunya Li is a professor in the College of Chemistry and Materials Science, South-
Central University for Nationalities. His current interests are nanomaterials, ionic
liquid and electrochemical sensors.
Dongyun Du is a professor in the College of Chemistry and Materials Science,
South-Central University for Nationalities. His current interests are environmental
sciences.
Xinyu Shen is associate professor in the College of Chemistry and Molecular Sci-
ences, Wuhan University. His current interests are material science.