Electrochimica Acta 140 (2014) 510

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Voltammetric Determination of Insecticide Thiamethoxam on Silver

Solid Amalgam Electrode
Parthena Chorti a , Jan Fischer b , Vlastimil Vyskocil b , Anastasios Economou a , Jiri Barek b,
a
National and Kapodistrian University of Athens, Department of Chemistry, Laboratory of Analytical Chemistry, Panepistimiopolis, Zografou,
157 71 Athens, Greece
b
Charles University in Prague, Faculty of Science, University Research Centre UNCE ,,Supramolecular Chemistry, Department of Analytical Chemistry,
UNESCO Laboratory of Environmental Electrochemistry, Albertov 6, CZ-128 43 Prague 2, Czech Republic

a r t i c l e

i n f o

Article history:
Received 14 November 2013
Received in revised form 13 January 2014
Accepted 14 January 2014
Available online 28 January 2014
Keywords:
Thiamethoxam
Differential pulse voltammetry (DPV)
Silver solid amalgam electrode
Solid phase extraction
Drinking water
River water

a b s t r a c t
This work demonstrates the applicability of differential pulse voltammetry (DPV) for the determination of
the insecticide thiamethoxam at a non-toxic mercury meniscus modied silver solid amalgam electrode
(m-AgSAE). The optimum supporting electrolyte was found to be Britton-Robinson (BR) buffer, pH 10. The
target compound was quantied directly in spiked drinking and river water samples in the range from
100 mol L1 to limits of determination (LOQs) 0.36 and 0.46 mol L1 , respectively. After preliminary
separation and preconcentration by solid phase extraction (SPE) using Lichrolut EN cartridges, quantication in spiked river and drinking water samples was possible in the range from 100 nmol L1 to LOQs
1.3 and 1.1 nmol L1 , respectively. m-AgSAE is practically non-toxic, possesses good mechanical stability
and is easy to handle and activate and thus represents a suitable alternative to the hanging mercury drop
electrode (HMDE).
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Over the last years, the use of pesticides in agriculture has
been instrumental in the increase in the agricultural production.
Although the presence of pesticides is currently not only necessary
but rather unavoidable, there are rising concerns about their excessive use and the potential side effects to human health, caused by
the consumption of food with pesticides residues.
Neonicotinoids are registered globally in more than 120
countries, representing nearly 25% of the global pesticide market,
and they are among the most effective insecticides for control of sucking insect pests. Thiamethoxam, (3-[(2-chloro-5-thiazolyl)methyl] tetrahydro-5-methyl-N-nitro-4H-1,3,5-oxadiazin-4imine, see Fig. 1) belongs to this group, and acts selectively on the
central nervous system of insects with minimal effects on benecial insects and with low toxicity toward mammals without causing
teratogenic or mutagenic effects [16]. Marked as Actara for foliar
treatment and as Cruiser for seed treatment, to date thiamethoxam
is registered for 116 types of crops in at least 64 countries
[1,5,7,8].

Corresponding author.
E-mail address: jiri.barek@natur.cuni.cz (J. Barek).
0013-4686/$ see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2014.01.081

Although thiamethoxam does not possess any toxicity for mammals, it has to be considered toxic to bees. In January 2013,
the European Food Safety Authority presented its conclusions
on the risk assessment for bees for three of the neonicotinoids
which are clothianidin, thiamethoxam and imidacloprid. According to this investigation, on May 2013 the European Union
voted for a two-year restriction on neonicotinoid insecticides
[9,10].
Consequently, the development of techniques for their determination is increasingly necessary. Several analytical methods have
been proposed for the determination of neonicotinoid insecticides
in foods, agricultural and environmental samples based on gas
chromatography (with prior derivatization) [11] and high performance liquid chromatography (HPLC) with UV [12], diode array
[1214], and mass spectrometric detection [11,1518] or ow
determination with amperometric (reductive pulsed mode) detection on nanoparticles modied glassy carbon electrode [19].
Different voltammetric methods have been developed for the
determination of thiamethoxam using several types of working
electrodes, summarized in Table 1 [1,5,6,8,19,20]. Relying on previous polarographic investigations, the detection of thiamethoxam
was based on the irreversible reduction of its nitro group. The shape
of the cathodic voltammograms depends on the pH of the medium,
which can be explained by the signicant role played by protons in
the reduction mechanism [7,20,21].

P. Chorti et al. / Electrochimica Acta 140 (2014) 510

Cl

O
H3C

S
N

N
NO2

Fig. 1. Structural formula of thiamethoxam.

Mercury electrodes are unique because of their high sensitivity, reproducibility, and wide cathodic potential window. However,
because of the fears of mercury toxicity, its use is currently
either regulated and/or even banned. As a consequence, non-toxic
electrode materials have appeared that are suitable for cathodic
determinations. Two groups, working independently, presented
various amalgam electrodes as viable alternatives to classical
mercury electrodes. The Trondheim group introduced the dental
amalgam electrodes [27] while Prague research group developed
electrodes based on metal amalgamated powders [22,23]. Several practical applications of theses electrodes have been reported
[22,2442]. The main advantages of the amalgam electrodes are
their wide range of working potentials, simple regeneration of the
electrode surface, rapid pretreatment procedure, long-term activity
without signicant changes in their sensitivity, mechanical stability, simple preparation in different sizes and shapes and low
toxicity, enabling their use in mobile laboratories and for measurements in owing systems (HPLC, FIA etc.). The preparation
of the mercury meniscus modied silver solid amalgam electrode
(m-AgSAE) is described in [25].
The aim of this work was to elaborate a sensitive and inexpensive voltammetric method using m-AgSAE and to verify its
applicability to the direct determination of thiamethoxam in real
water samples. The attempt to achieve nanomolar concentration
levels has prompted the use of solid phase extraction (SPE) for
preliminary separation and preconcentration of this insecticide.
2. Experimental
2.1. Chemicals and Reagents
The analytical standard of thiamethoxam (Sigma-Aldrich,
Germany) was of purity 99.7%. A 1.0 103 molL1 stock solution of the substance was prepared in double deionized water.
Britton-Robinson (BR) buffers were prepared by mixing a solution of 0.04 mol L1 in phosphoric acid, 0.04 mol L1 in acetic acid
and 0.04 mol L1 in boric acid with the appropriate amount of
0.2 mol L1 sodium hydroxide solution. Potassium chloride and
ethyl acetate were supplied by Lachner, Neratovice, Czech Republic,
sodium hydroxide was from Penta (Czech Republic) and methanol
was provided by Merck (Germany). Deionized water was produced by a Milli-Q plus system (Millipore, Billerica, MA, USA). All
the chemicals were used without further purication and all the

solutions were stored in glass vessels in the dark at laboratory

temperature.
LiChrolut EN SPE cartridges (200 mg) were purchased from
Merck (Germany). They are lled with highly cross-linked
ethylvinylbenzene-divinylbenzene copolymer, an outstanding sorbent with a specic surface area of approximately 1200 m2 g1 ,
that shows hydrophilic properties without any surface modication. Due to its micro-porous structure (particles of 10120 m),
it exhibits a high adsorptive capacity, about 10 times higher than
C-18 phase [18].

2.2. Water Samples

The drinking water sample was collected from the tap of Department of Analytical Chemistry of Charles University in Prague,
Hlavova 2030/8, CZ 12843 Prague 2 and the river water sample was collected from Vltava river, at Ciheln street, Praha-Mal
Strana, Czech Republic. For measurements with SPE preconcentration, river water samples were ltered through lter paper of pore
size 14 m (Filtrak, Grade 388, Germany).

2.3. Apparatus
Voltammetric measurements were carried out using a computer
controlled Eco-Tribo-Polarograph with Polar Pro software version
5.1 (both from Polaro-Sensors, Prague, Czech Republic) with a
three-electrode system in a 10 mL glass vessel. The three-electrode
system comprised platinum auxiliary electrode PPE (Monocrystals
Turnov, Czech Republic), silver/silver chloride (Ag|AgCl (3 M KCl),
Type 10-20+, Electrochemical Detectors, Turnov, Czech Republic)
reference electrode and m-AgSAE (2-0907, 0.5 mm diameter, J. Heyrovsky Institute of Physical Chemistry of the AS CR, v.v.i., Prague,
Czech Republic) working electrode. The software worked under the
operational system Microsoft Windows XP Professional (Microsoft
Corporation). The pretreatment of the m-AgSAE consisted of three
steps: amalgamation, electrochemical activation and electrochemical regeneration. These procedures are described in previous work
[25].
Scan rate of 20 mV s1 , pulse amplitude of 50 mV and a pulse
width of 100 ms were used in DPV; for direct current voltammetry
(DCV), the same scan rate was used. Oxygen was removed by passing nitrogen (purity 99.99%, Linde Praha, Prague, Czech Republic)
through the solution for 5 min. All experiments were conducted at
laboratory temperature.
Spectrophotometric measurements were performed with an
Agilent 8453 UV-Vis spectrophotometer driven by the UV-Visible
ChemStation 9.01 software (both Agilent Technologies, Santa Clara,
CA, USA) in absorption quartz cuvettes with an optical path length
of 10 mm (Hellma, Mllheim, Germany). The wavelength of the
measurements in methanol (MeOH) was 254 nm, in ethyl acetate
(ETA) 258 nm and in the mixture MeOH/ETA (50:50) was 256 nm.
pH values of the prepared BR buffers were measured by a digital

Table 1
Comparison of LOQs for the voltammetric determinations of thiamethoxam on various electrodes.
Method

Electrode

LOQ (molL1 )

Ref.

Cyclic voltammetry
DPV
DPV
Differential pulse polarography
DPV
Square-wave voltammetry
Square-wave voltammetry
Cyclic voltammetry
DPV

Glassy carbon electrode (GCE)

Bismuth lm electrode
Mercury lm electrode
Dropping mercury electrode
Tricresyl phosphate-based carbon paste electrode
Hanging mercury drop electrode
Silver amalgam lm electrode
Nanosilver/surfactant modied GCE
Nanosilver/surfactant modied GCE

95.0
4.3
2.6
0.1
1.3
3.1
2.4
15.9
0.4

[1]
[20]
[20]
[5]
[6]
[8]
[8]
[19]
[19]

P. Chorti et al. / Electrochimica Acta 140 (2014) 510

pH-meter (Type 3510, Jenway, UK) using a combined glass electrode.

For the SPE, a rotary evaporator (Type Rotavapor EL 130, Buchi,
Germany) was used.

-300

2.4.2. Differential pulse voltammetry after solid phase extraction

The SPE cartridge was conditioned by 3 mL of methanol and 3 mL
of deionised water. Afterwards, water sample was passed through
it at a ow rate of 10 mL min1 and the cartridge was washed with
10 mL of deionized water. The cartridge was dried by a ow of air
for 20 min and thiamethoxam was eluted with 3 mL of the selected
eluent. The solvent was evaporated to dryness with a rotary evaporator; the residue was dissolved in 1 mL of BR buffer, pH 10,
transferred to specially adapted voltammetric vessel enabling the
measurement of 1 mL of tested solution and subjected to DPV at a
m-AgSAE.
2.4.3. Evaluation of measurements
DPV peaks were evaluated from the straight line connecting
the minima before and after the peak, if not stated otherwise.
All the curves were measured ve times. The calibration curves
parameters (e.g. slope, intercept, limit of determination) were calculated using OriginPro 7.5 software and the limit of determination
(LOQ) was calculated using the equation: LOQ = 10s/b, where s is the
standard deviation of the lowest measurable concentration of 12
repetitive measurements and b is the slope of the calibration curve
[43].
Recovery of thiamethoxam was calculated using the ratio of the
DPV peak height of the compound in the extract (i.e. after subjecting
the spiked sample to SPE) to the DPV peak height of a standard
thiamethoxam solution of identical concentration.

-1100

I, nA

Ep, mV
-800

-200

4
2

2.4. Procedures
2.4.1. Direct differential pulse voltammetry
The general procedure for the voltammetric investigations
was as follows: the required amount of the stock solution of
thiamethoxam in deionized water was measured into a 10 mL
voltammetric ask and the solution was diluted to the mark with
BR buffer of the required pH. The solution was transferred into
the voltammetric cell, deoxygenated by bubbling with nitrogen for
5 min and the voltammogram was recorded.
Drinking or river water samples were spiked by known amounts
of thiamethoxam standard solutions resulting in the concentration
range from 0.2 to 120 mol L1 of thiamethoxam in model samples.
Afterwards, 9.0 mL of model water sample and 1.0 mL of BR buffer
of pH 10.0 were mixed, bubbled with nitrogen and subjected to DPV
at m-AgSAE.

12

pH

3 7
6

10

-100

89 5

11
12

-500

-800

-1100

E, mV

Fig. 2. DC voltammograms of thiamethoxam (c = 1.0104 mol L1 ) at m-AgSAE

(without regeneration of the electrode) in BR buffer pH 2.0 12.0 (pH is given above
voltammogram). Dependence of DCV peak potentials on pH of BR buffer is in inset.

media, a two-step mechanism could be proposed, corresponding to

the reduction of the nitro group of thiamethoxam to hydroxylamine
[21].
The highest, best developed, and most easily evaluated peak
was the rst peak obtained at pH 9.0 for DCV or at pH 10.0 for
DPV. Therefore, these peaks were used for subsequent measurements. For comparison, the instability was observed under these
conditions on silver amalgam lm electrode [8]. Electrochemical
regeneration was necessary only for DPV experiments. The optimum values of the two regeneration potentials Reg1 and Reg2 were
found experimentally as the values leading to most stable signal
values in repeated measurements. A value of +120 mV was selected
for Ereg1 , and -1700 mV for Ereg2 . Regeneration lasting about 30 s
was based on application of 300 polarizing cycles (switching the
electrode potential from +120 mV to -1700 mV for 50 ms. Regeneration pretreatment was not necessary for DCV. The reproducibility
of the measurements expressed in terms of the % relative standard
deviation (% RSD) of the peak current (Ip ) values, evaluated from
20 successive voltammetric measurements at the m-AgSAE, was
found to be 1.9% for DPV and 0.68% for DCV.
Under the optimum conditions found, DCV and DPV calibration curves were constructed over the concentration range from
0.2 to 120 molL1 of thiamethoxam in BR buffer pH 10 (DPV) and
9 (DCV), respectively. It follows from Table 2 that the LOQ of DCV
was higher than that of DPV. Therefore, DPV was used for further
measurements.
It should be mentioned that an attempt to increase the sensitivity by adsorptive accumulation of the analyte on the surface of the
working electrode was not successful probable because of its good
solubility in water. (1 molL1 thiamethoxam in BR buffer pH 10.0,
accumulation potentials from 0 to -800 mV and accumulation times

3. Results and Discussion

-300

3.1. Direct differential pulse voltammetry of thiamethoxam

For optimization of direct current voltammetry (DCV) and differential pulse voltammetry (DPV) at a m-AgSAE, a 1.0 104
molL1 solution of thiamethoxam in BR buffer at different pH values
from 2.0 to 12.0 (Figs. 2 and 3) was used. Only one peak was evident
in the whole pH range studied, except in pH range 2 7 for DCV
(inset of Fig. 2) or in pH range 4 9 for DPV (inset of Fig. 3) in which
a second peak also appeared. The peak potentials of both peaks
were shifted to more negative values with increasing pH. These
results are well comparable with previous square-wave voltammetric investigations at a renewable silver amalgam lm electrode
[8] and can be explained by the participation of protons in the electrochemical reduction of thiamethoxam. Based on previous review
on the reduction of the nitro group containing pesticides in alkaline

-1400

I, nA

Ep , mV9
-1100

-200

-800
2

4
2 3

-100

pH

12

-500

10

11
12

67

-800

-1100

E, mV

-1400

Fig. 3. DP voltammograms of thiamethoxam (c = 1.0104 mol L1 ) at the m-AgSAE

(without regeneration of the electrode) in BR buffer pH 2.0 12.0 (pH is given above
voltammograms). Dependence of DPV peak potentials (1st and 2nd peak) on the pH
of BR buffer is presented in the inset.

P. Chorti et al. / Electrochimica Acta 140 (2014) 510

Table 2
Parameters of the calibration straight lines for the direct determination of thiamethoxam by DCV or DPV at m-AgSAE in deionized, drinking and river water. (Ereg1 = +120 mV,
Ereg2 = 1700 mV).
c (moll1 )

Slope (nAmol1 L)

DCV at m-AgSAE, BR buffer pH 9.0-deionized water (1:9) mixture

-1.65
20120
210
-4.67
0.61
-5.70
DPV at m-AgSAE, BR buffer pH 10.0-deionized water (1:9) mixture
-2.16
20120
-2.53
210
-2.89
0.21
DPV at m-AgSAE, BR buffer pH 10.0-drinking water (1:9) mixture
20120
-1.35
210
-2.44
0.41
-3.17
DPV at m-AgSAE, BR buffer pH 10.0-river water (1:9) mixture
-1.40
20120
-2.22
210
-2.59
0.41
a

Intercept (nA)a

LOQ (mol L1 )

-23.31
-2.84
-4.02

-0.9805
-0.9997
-0.9999

0.56

-8.46
-0.70
0.13

-0.9993
-0.9982
-0.9967

0.26

-21.17
-0.41
+0.16

-0.9868
-0.9993
-0.9999

0.36

-14.36
-0.21
-0.22

-0.9948
-0.9993
-0.9999

0.46

Intercepts were statistically tested at the signicance level 0.05 and it was found that they are statistically different from zero

from 0 to 120 sec were tested. However, no signicant increase of

peak current was observed).

-5
I, nA

6
5

-4

3.2. Direct voltammetric determination of thiamethoxam in

drinking and river water
The practical applicability of the newly developed method was
demonstrated by the direct determination of thiamethoxam in
model samples of drinking and river water. Drinking or river
water samples were spiked by known amounts of thiamethoxam
standard solutions resulting in the concentration range from 0.2 to
120 molL1 of thiamethoxam in model samples.
DP voltammograms representing the direct determination of
thiamethoxam in spiked river and drinking water for the range from
0.2 to 1 molL1 are given in the Fig. 4. Lowest measured concentration was found under LOQ. The parameters of the calibration curves
obtained are summarized in Table 2. It can be seen that even submicromolar concentration can be reliable determined in the simple
environmental matrix using the newly developed method.
3.3. Differential pulse voltammetric determination of
thiamethoxam after solid phase extraction
To reach nanomolar concentration region by the newly developed method, it is necessary to use preliminary separation and
preconcentration using solid phase extraction (SPE).
For the selection of optimum eluent for thiamethoxam, recoveries were tested by UV-Vis spectrophotometry. 100 mL of deionized
water samples containing 5.0 106 molL1 of thiamethoxam
were extracted using LiChrolut-EN cartridges pre-conditioned with
3 mL of methanol and 3 mL of deionized water. The samples were

4
3

-3

-5
-3

I, nA

I , nA
p
-2
-1

-4

0
0.0

0.6

1.2

-800

6
5
4

-3

Ip, nA

-2
-1
0
0.0

-1
c, mol.L

-3

-2

0.6

-1
c, mol.L

1.2

2
1

-1000

E, mV

-1200

-2
-800

-1000

E, mV

-1200

Fig. 4. DP voltammograms of thiamethoxam at m-AgSAE in spiked river water (A)

and drinking water (B) - BR buffer pH 10.0 mixture (9:1) Concentration of thiamethoxam in the water samples (mol L1 ): 0 (1), 0.2 (2), 0.4 (3), 0.6 (4), 0.8 (5) and
1.0 (6). Ereg1 = +120 mV, Ereg2 = 1700 mV. Corresponding calibration dependence is
shown in the inset.

sucked through the column at a ow rate of 10 mL min1 and the

cartridges were washed with 10 mL of deionized water. After drying SPE column properly, thiametoxam was eluted with 5 mL of
tested solvent (methanol (MeOH), ethyl acetate (ETA), and the mixture of MeOH/ETA 50:50 (v/v) with recoveries 60 1 %, 82.0 0.3 %
and 91 2 %, respectively). UV-Vis spectrophotometry was used to
determine the analyte recovery. The recovery was found from the
comparison of the ratio of the solution absorbance after SPE divided
by the absorbance of standard solution of equal concentration.
It is obvious that the best recovery was obtained with mixture of
MeOH/ETA 50:50 (v/v), which is in agreement with reference [18].
Afterwards, SPE recovery was determined by DPV at m-AgSAE.
The recovery from three parallel experiments was found to be 98%
for SPE from 100 mL of deionized water containing 1 molL1 of

Table 3
Parameters of the calibration straight lines for the DPV determination of thiamethoxam at m-AgSAE in deionized, drinking and river water after SPE in BR buffer pH 10.0
(Ereg1 = +120 mV, Ereg2 = 1700 mV).
Extracted volume
Deionized water
100 mL
1L
Drinking water
100 mL
1L
River water
100 mL
1L
a

c (nmolL1 )

Slope (nA nmol1 L)

Intercept (nA) a

LOQ
(nmol L1 )

20100
210

-0.228
-1.89

-2.98
-2.63

-0.9989
-0.9961

12.2
2.0

20100
210

-0.188
-1.87

-0.41
-0.02

-0.9989
-0.9978

15.5
1.1

20100
210

-0.197
-2.06

0.02
1.74

-0.9986
-0.9977

11.4
1.3

Intercepts were statistically tested at the signicance level 0.05 and it was found that they are statistically different from zero

P. Chorti et al. / Electrochimica Acta 140 (2014) 510

-50

-20

I, nA
-40

I , nA
p

-10

0
0

-30

50

100

-1

c, nmol.L

-10

5
4
3
2
1

I , nA
p

-50

I, nA

4
3
2

-20

0
0

-30

10

-1

c, nmol.L

-20
-900

-1100

E, mV

-1300

-10
-900

B
-1100

E, mV

-1300

Fig. 5. DP voltammograms of thiamethoxam at m-AgSAE in BR buffer pH 10.0, measured in 1 mL cell after SPE from 100 mL of drinking water (A) and from 1000 mL of
river water (B). For drinking water, concentration of thiamethoxam in model sample
was c(nmol L1 ): 0 (1), 20 (2), 40 (3), 60 (4), 80 (5) and 100 (6). For river water it was
c(nmol L1 ): 0 (1), 2 (2), 4 (3), 6 (4), 8 (5) and 10 (6). Ereg1 = +120 mV, Ereg2 = 1700 mV.
Corresponding calibration dependence is depicted in the inset.

thiamethoxam and 80% for SPE from 1L of deionized water containing 0.1 molL1 of the analyte. The recovery was found to be
74% for SPE from both 100 mL and 1 L of river water containing
1 molL1 and 0.1 molL1 of the analyte. For drinking water, the
analogous recoveries were found to be 73% and 75%, respectively.
The LOQs and the parameters of the calibration curves for the DPV
at m-AgSAE after SPE are given in the Table 3.
Fig. 5 shows the well-developed voltammograms with peak
currents directly proportional to nanomolar concentration of thiamethoxam.
4. Conclusion
In this work, it has been demonstrated that m-AgSAE can be used
for the determination of thiamethoxam. The lowest determination
limits were obtained using DPV in BR buffer pH 10. The applicability
of the m-AgSAE was also conrmed for the direct measurements
in drinking and river water. It conrms that inorganic compounds
normally present in drinking and river water do not interfere with
voltammetric determination of thiamethoxam at m-AgSAE. Satisfactory recoveries of SPE even in nanomolar concentration range
were received for these environmental matrices. The LOQs for thiamethoxam using an enrichment factor of 1000 were 1.3 and 1.1
nmol L1 for river and drinking water, respectively. In comparison with silver amalgam lm electrode [8], we have received with
m-AgSAE signicantly higher sensitivity which could be linked to
higher robustness of m-AgSAE in comparison with amalgam lm
electrode used in paper [8]. The possibility of voltammetric determination of other neonicotinoids using m-AgSAE is under further
investigation including possible interference of individual neonicotionoids and their possible simultaneous determination.
Acknowledgement
The research was nancially supported by Grant Agency of the
Czech Republic (project P206/12/G151) and by GreeceCzech Bilateral Cooperation Program (project 7AMB12GR003).
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