Sensors and Actuators B 181 (2013) 294–300

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Sensors and Actuators B: Chemical

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Green electrochemical sensor for environmental monitoring of pesticides:

Determination of atrazine in river waters using a boron-doped diamond electrode
L’ubomír Švorc ∗ , Miroslav Rievaj, Dušan Bustin
Institute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, Bratislava, SK-812 37, Slovak Republic

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

Article history: A novel, simple and sensitive electrochemical method for the determination of atrazine using a square-
Received 28 December 2012 wave voltammetry on boron-doped diamond electrode was developed. Atrazine provided a single well-
Received in revised form 4 February 2013 defined reduction peak at −1.1 V vs. Ag/AgCl electrode in Britton–Robinson buffer solution at pH 3. The
Accepted 7 February 2013
effect of supporting electrolyte, pH and scan rate on the current response of atrazine was studied to select
Available online 16 February 2013
the optimum experimental conditions. The linear concentration range from 0.05 to 40 ␮M (R2 = 0.999,
n = 6), the good repeatability (relative standard deviation of 2.9% at 10 ␮M for n = 6) and the detection
Keywords:
limit of 10 nM were achieved at optimized square-wave voltammetric parameters (step potential of 5 mV,
Atrazine
Boron-doped diamond electrode
frequency of 60 Hz and amplitude of 80 mV). The influence of possible interfering agents appeared to be
Mercury electrode minor which evidently proved the good selectivity of method. The proposed method was successfully
Square-wave voltammetry applied for the determination of atrazine in spiked river water samples with satisfactory recoveries (92 to
River water 100%) and the good agreement to results obtained by reference high performance liquid chromatography
Environmental monitoring method at confidence interval for 95% probability. In this way, boron-doped diamond could represent
an environmentally acceptable (green) alternative to highly toxic mercury electrodes for monitoring of
pesticides.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction of the hormonal system [4]. ATZ is classified as a priority pol-

Nowadays, the large amounts of various harmful chemicals
are used in agriculture. These substances (usually organic com-
pounds such as herbicides, insecticides and fungicides) are very
persistent in the environment and their prolonged use involves
the hazards of retention in soils. Subsequently they could pass
into surface and ground waters due to washing and leaching pro-
cesses. From these reasons, an enhancing attention is given to the
increase of health risks associated with exposure of human popu-
lation to harmful substances occurring in the environment. Their
monitoring is one of the most important tasks of modern analytical
chemistry [1].
Atrazine (IUPAC name: 6-chloro-N-ethyl-N -isopropyl-1,3,5-
triazine-2,4-diamine; ATZ) is the most known triazine herbicide
with toxic effects on aquatic organisms. It has been used in the
annual control of some grasses and broadleaf weeds in corn, sugar
cane, pineapple, pinus and other cultures. Due to its low reactivity,
water solubility and slow degradation, ATZ is reasonably stable,
mobile and persistent in the environment for a longer period (half
life varying among 20 and 100 days) [2,3]. In very small quantities,
it may act as a carcinogen of type C and an endocrine disruptor
∗ Corresponding author. Tel.: +421 (0)2 59325302; fax: +421 (0)2 59325590.
E-mail address: lubomir.svorc@stuba.sk (L’. Švorc).
lutant which use in agriculture is currently prohibited according
to the EC legislation (Commission Decision 2004/248/EC) [5] as
well as to the Slovak legislation (Parliamentary Act No. 364/2004
Coll., Government Ordinance No. 296/2005 Coll.). This herbicide
belongs to the list of dangerous substances in Slovak Republic,
whereby it has been considered within the document for lower-
ing of water pollution especially by toxic and harmful compounds
[6]. Because of these objectives, there is a still growing need for
the development of sensitive and selective analytical methods
for environmental monitoring of residual amounts of (prohibited)
pesticides.
A literature research shows many reports describing vari-
ous analytical methods for the determination of ATZ and other
triazine herbicides in recent years. These particularly involve spec-
trophotometric [7] and especially chromatographic methods such
as high performance liquid chromatography (HPLC) [8–11] and
gas chromatography (GC) [12–14] which have become the most
widely used analytical methods for determination of trace amounts
of triazine herbicides because of their absolute best sensitivity
and selectivity. However, these techniques require the compli-
cated sample preparation usually involving the pre-concentration
step prior to the analysis. In addition, they are expensive, time-
consuming, solvent waste-producing as well as the demands for
highly skilled personnel often restrict their use in routine analytical
practice.

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http://dx.doi.org/10.1016/j.snb.2013.02.036
 L’. Švorc et al. / Sensors and Actuators B 181 (2013) 294–300
The electrochemical methods are especially suitable for the
environmental monitoring of heavy metals and electroactive
organic pollutants. They are simple, inexpensive, sufficiently sensi-
tive as well as they can represent an independent alternative to so
far dominant spectrophotometric and chromatographic techniques
[1]. Regarding the determination of ATZ, the enzyme biosensors and
immunosensors are used [15,16] or processes occurring on mer-
cury electrodes, such as hanging mercury drop electrode (HMDE)
[17–19], static mercury drop electrode (SMDE) [20–22] and mer-
cury film electrode (MFE) [23] are mostly exploited. These methods
belong to the most sensitive ones thanks to the excellent elec-
trochemical properties of mercury. On the other hand, the highly
toxic nature of mercury insists on the necessary search for the
alternative electrode materials. Therefore, the novel, simple and
environmentally acceptable electrochemical tool for the sensitive
environmental monitoring of pesticide residues is great of impor-
tance. The several solid electrode surfaces have been proposed for
the determination of pesticides with the main target of avoiding the
use of mercury. In this context, the solid amalgam electrodes are
used due to the mechanic stability, easy preparation and nontoxic-
ity. They also have solid and homogeneous surfaces that allow easy
renewal by mechanical polishing and minimize the environmental
mercury contamination since the amount of mercury discarded in
analysis is minimal [24]. Bismuth film [25] and carbon paste elec-
trodes either bare or modified [26,27] have also been designed in
order to produce electroactivity for the detection and quantification
of pesticides.
Generally, an irreversible adsorption of products of electrode
reaction resulting in the passivation layer usually occurs in the
electrochemical measurements. By the end of 20th century, a
boron-doped diamond (BDD) as the new perspective carbon-based
electrode material was discovered [28,29]. This electrode has the
minimal noise due to the low residual current, good mechanical
robustness, stability in both alkaline and acidic media, biocom-
patibility, the widest usable potential range from all electrode
materials (up to 3 V) and minimal problems with passivation per-
tinent to sp3 character of diamond carbon [30]. The development
of new electrochemical methods using BDD electrode can provide
the invaluable services in the monitoring of compounds impor-
tant in terms of protection of human health, environment and food
chemistry. The recent reports of our working group have shown
that several important biomolecules are able to be satisfactorily
determined using BDD electrode [31–34].
In this paper, the voltammetric determination of ATZ using
square-wave voltammetry on BDD electrode is described. Gener-
ally, to the best of our knowledge, the detection and determination
of ATZ on this perspective and environmentally acceptable elec-
trode material has not been previously investigated in literature
with the exception of oxidation on BDD electrode for the miner-
alization of triazines including ATZ [35]. The practical applicability
of proposed method is demonstrated in the determination of ATZ
in spiked river water samples. The developed procedure could also
find an application in environmental monitoring of other harmful
organic compounds thanks to rapidity, simplicity and sensitivity.
2. Experimental
2.1. Chemicals
ATZ standard (CAS No. 1912-24-9, purity of 99%) was obtained
from Sigma–Aldrich (Slovak Republic) and used as received without
any further purification. The studied supporting electrolytes were
hydrochloric acid, acetic acid, acetate buffer, phosphate buffer and
Britton–Robinson buffer solution (Lachema Brno, Czech Republic).
Britton–Robinson buffer solution was prepared from a mixture of
295
phosphoric acid (pKa 2.14, 7.20 and 12.15), acetic acid (pKa 4.75)
and boric acid (pKa 9.24, 12.74 and 13.80), with all components at
concentration of 40 mM and adjusting to the required pH value with
sodium hydroxide (0.2 M). All other chemicals were of analytical
grade purity. Stock solution of ATZ (1 mM) was prepared by disso-
lution of solid standard in 5 mL of methanol and then diluted with
double-distilled deionized water with resistivity above 18 M cm.
Working and calibration solutions of lower concentrations of ATZ
were freshly prepared by diluting with supporting electrolyte. Ace-
tonitrile (Merck, Czech Republic) was used as organic component
in mobile phase for the purposes of HPLC analysis.
2.2. Apparatus
The voltammetric measurements were performed with an
AUTOLAB PGSTAT 302 N (Metrohm Autolab B.V., The Netherlands)
potentiostat/galvanostat controlled by NOVA 1.9 electrochemical
software. The three electrode system consisted of Ag/AgCl/3 M KCl
and platinum wire as reference and counter electrode, respec-
tively. BDD electrode inserted in polyether ether ketone (PEEK)
body with disk inner diameter of 3 mm, resistivity of 0.075 cm
and boron doping level of 1000 ppm (declared by Windsor Scientific
Ltd, United Kingdom as manufacturer) was used as working elec-
trode. The glassy carbon (GC) with disk diameter of 2 mm was used
as comparative working electrode (Metrohm, Slovak Republic). All
the pH values of solutions were measured using pH meter Model
215 (Denver Instrument, USA) with combined electrode (glass-
reference electrode), which was daily calibrated with standard
buffer solutions. All the potentials reported in this paper were given
against Ag/AgCl/3 M KCl reference electrode at a laboratory temper-
ature of 25 ± 1 ◦ C.
The determination of ATZ by HPLC as a reference (compara-
tive) method was carried out using a Young Lin 9100 system, with
Photodiode Array (PDA) detector set at 220 nm. A GraceSmart RP-
18 (6.0 mm × 150 mm, 5 ␮m) chromatographic column was used.
The mobile phase was mixture of acetonitrile–water (30:70, v/v) at
flow rate of 1.0 mL min−1 , while the injection volume was 10 ␮L.
2.3. Measurement procedures
A particular volume of standard solution of ATZ was pipetted
into a 20 mL volumetric flask, then filled up with the supporting
electrolyte and transferred quantitatively into voltammetric cell.
Cyclic voltammetry (CV) and square-wave voltammetry (SWV)
were employed for optimization study and quantification of
ATZ, respectively. Ultrapure N2 (O2 < 2 ppm) was used to remove
dissolved O2 from each solutions and to provide an inert atmo-
sphere inside the voltammetric cell. Five CV voltammograms were
obtained for each measurement, and the last scan was always con-
sidered for evaluation and making the figures reported in this paper.
SW voltammograms were recorded after optimization of instru-
mental parameters (step potential, frequency and amplitude). The
peak currents (Ip ) recorded using CV and SWV were evaluated from
the straight lines connecting the minima before and after the peak
maximum without background correction. In order to clean BDD
electrode surface prior to start the first voltammetric measurement,
CV measurements were performed from −2 to +2 V vs. Ag/AgCl elec-
trode for 10 min in 1 M HNO3 . After this procedure, BDD electrode
was rinsed with deionized water and polished with a piece of damp
silk cloth until a mirror-like character of surface was attained. Cal-
ibration curve was constructed from the average of six replicate
measurements for each calibration solution of ATZ and analyzed by
linear least-square regression in OriginPro 8.0 (OriginLab Corpora-
tion, USA) with the relevant results (slope and intercept) reported
with confidence interval for 95% probability. The detection limit
was calculated as three times the standard deviation for the blank
296 L’. Švorc et al. / Sensors and Actuators B 181 (2013) 294–300

solution (supporting electrolyte) divided by the slope of the cali-

bration curve.

2.4. Preparation of river water samples spiked with ATZ

The water samples (S1–S3) were obtained from three Slovak

rivers: Danube (S1), Váh (S2) and Nitra (S3) flowing through cities:
Bratislava, Sered’ and Nitra, where the samples were collected.
Each water sample was filtered through a filter paper to obtain a
clear filtrate, then quantitatively transferred into 100 mL volumet-
ric flask and stored in a fridge at 7 ◦ C. The determination of ATZ
in river water samples was performed as follows: the calculated
amount of standard solution of ATZ was added to the volumetric
flask containing 5 mL of river water and 15 mL of Britton–Robinson
buffer solution at pH 3. After this procedure, the solution was
stirred in order to homogenize and bubbled with ultrapure N2 Fig. 1. CV voltammograms of 0 (blank) and 10 ␮M ATZ in BRBS at pH 3 on BDD and
(O2 < 2 ppm) to remove dissolved O2 . The river water spiked with GC electrode in potential range from 0 to −2 V with scan rate of 100 mV s−1 .
ATZ was analyzed by the standard addition method in order to
reduce the matrix effect using the conditions described in previous
sections.

3. Results and discussion

3.1. Voltammetric behavior of ATZ on BDD electrode

3.1.1. Effect of supporting electrolyte

The choice of the supporting electrolyte is an important stage
in electroanalytical studies because its composition and pH influ-
ence the properties of the analyzed solution as well as the
electrode–solution interface, modifying the thermodynamics and
kinetics of the charge transfer process [36]. The effect of suppor-
ting electrolytes with different compositions and pH values was
investigated using CV in order to choose the best medium for the
voltammetric determination of ATZ on BDD electrode. For this pur-
pose, hydrochloric acid (HCl), acetic acid (CH3 COOH), acetate buffer
(ABS), phosphate buffer (PBS) and Britton–Robinson buffer solu-
tion (BRBS) were studied (CV voltammograms not shown). The
most favorable results arising from the current response of ATZ (the
most sensitive and well-defined voltammetric peak) were accom-
plished in BRBS at pH 3, while HCl and CH3 COOH represented the
media with poor sensitivity to ATZ. ABS and PBS were consid-
ered to be better media than studied acids but not as sensitive
as BRBS. Hence, BRBS was chosen as the most suitable suppor-
ting electrolyte in all subsequent voltammetric experiments in this
work.
3.1.2. Comparison of BDD with GC in voltammetric behavior of
ATZ
ATZ is electroactive compound with peak maximum at relatively
high negative potential. In order to evaluate the advantages of the
use of BDD electrode with respect to other carbon-based materials,
CV experiments were performed to study the voltammetric behav-
ior of ATZ on bare electrodes, investigating both GC and BDD. Fig. 1
allows the comparison of CV voltammograms in the absence (blank)
and presence of 10 ␮M ATZ in BRBS at pH 3 on GC and BDD electrode
in potential range from 0 to −2 V. It is evident that both electrodes
provided sufficiently sensitive current responses of ATZ while those
observed on bare BDD showed remarkable (approximately three
times) higher peak current with respect to the GC electrode. The
registered CV voltammograms implied that the single well-defined
voltammetric peak appertaining to reduction of ATZ appeared at
potential −1.1 V vs. Ag/AgCl electrode. On the reverse scan, the
absence of corresponding oxidation peak was observed indicat-
Fig. 2. Effect of pH on the peak potential () and peak current () of 10 ␮M ATZ in
BRBS on BDD electrode using CV with scan rate of 100 mV s−1 .
and obsolete mercury electrodes [17–19] as well as nontoxic solid
amalgam electrode [24]. It is also apparent that the residual cur-
rent appeared to be sufficiently low at higher negative potentials
on BDD electrode when compared with GC electrode. Moreover, we
also observed the high hydrogen overpotential, because the gener-
ation of hydrogen bubbles did not occur even at potential of more
than −1.8 V vs. Ag/AgCl electrode on BDD electrode. This value was
significantly higher than in the case of GC electrode where the bub-
bles of hydrogen occurred at about −1.5 V. These facts confirm the
advantage of the use of BDD electrode. Additional information from
Fig. 1 concerns the peak potential of ATZ, which remains the same at
both electrode surfaces, indicating that analogous reduction mech-
anisms were attained.
3.1.3. Effect of pH
Generally, the effect of pH of supporting electrolyte on the cur-
rent response of monitored analyte plays the important part in
its detection and quantification [37]. Concerning ATZ, the studied
pH range was from 2 to 7 using BRBS because the electrochemical
reduction of ATZ does not take place in alkaline aqueous media. It
Table 1
Optimized SWV instrumental parameters for determination of ATZ.
Instrumental parameter Studied range Level of change Optimum value

ing that electrode process of ATZ is a totally irreversible one on Amplitude (mV) 20–120 10 80
both electrode surfaces. The electrochemical behavior of ATZ on Frequency (Hz) 10–100 10 60
Step potential (mV) 1–10 1 5
carbon-based electrodes well agrees with those reported for toxic
 L’. Švorc et al. / Sensors and Actuators B 181 (2013) 294–300 297

Table 2
Analytical parameters for determination of ATZ in BRBS at pH 3 using proposed method.

Analyte Linear range (␮M) Linear regression equation (I: ␮A, cATZ : ␮M) R2 LOD (nM) RSDa (%)

ATZ 0.05–40 IATZ = −0.092(±0.002) − 0.622(±0.016)cATZ 0.999 10 2.9

a
Calculated for 6 replicate SWV measurements at 10 ␮M ATZ.

was found that the peak potential (Ep ) of ATZ shifted to more nega-
tive potentials with the increase of pH of supporting electrolyte as
depicted in Fig. 2. The relationship between Ep and pH is expressed
as equation (Eq. (1)):

Ep (V) = −0.895(±0.013) − 0.067(±0.003)pH (R2 = 0.991) (1)

The slope of this equation is 67 mV per unit of pH suggesting

the involvement of one proton in the rate-limiting step. This fact
is in good agreement with the results reported for the reduction
process of ATZ on mercury electrode surfaces [31,32]. Moreover,
the detailed study of electrochemical reduction of ATZ and other
triazines has been reported by Pospíšil et al. [38] who suggested
the mechanism based on the reduction of the carbon-chloride bond
with the previous protonation of nitrogen in triazine ring before
electron transfer. The effect of pH on the peak current (Ip ) was also
studied in the pH range of 2–7 as shown in Fig. 2. It can be observed
that the peak current shows a maximum for pH 3 leading us to the
opinion that this is the optimum pH value for further voltammetric Fig. 4. SW voltammograms of various ATZ concentrations in BRBS at pH 3 on BDD
electrode: (a) 0, (b) 0.05, (c) 0.2, (d) 1, (e) 3, (f) 5, (g) 7, (h) 10, (i) 20, (j) 30 and
measurements.
(k) 40 ␮M. The optimized SWV instrumental parameters: step potential of 5 mV,
frequency of 60 Hz and amplitude of 80 mV. The dependence between peak current
(␮A) and ATZ concentrations (␮M) appears in the inset.
3.1.4. Effect of scan rate
The useful information including the mechanism of electrode
3.2. Analytical performance
reaction (rate-limiting step) may be acquired from the relation-
ship between the peak current and scan rate (v). The effect of
3.2.1. Effect of SWV instrumental parameters
scan rate on the peak current of ATZ was examined in the range
SWV is a pulse voltammetric technique that offers the advantage
0.015–0.150 V s−1 in BRBS at pH 3 using CV on BDD electrode as
of rapidity (analysis time in a few seconds in comparison with dif-
shown in Fig. 3. The peak current of 10 ␮M ATZ increased linearly
ferential pulse voltammetry) and excellent sensitivity connected
with the square root of scan rate (inset of Fig. 3) and this relation is
with effective discrimination against the capacitive current. This
represented by Eq. (2). These observations suggest that the diffu-
technique has been applied for determination of trace amounts
sion plays the significant role in the irreversible electrode reaction
of numerous electroactive organic compounds in environment.
of ATZ on BDD electrode.
The optimization of the SWV instrumental parameters that may
influence the current response of analyte is a significant step in
IATZ (␮A) = −0.053(±0.002) − 33.071(±0.768)v1/2 (Vs−1 )
the development of the electroanalytical methodology. Hence, the
× (R2 = 0.997) (2) instrumental parameters such as step potential, frequency and
amplitude were examined in order to find the optimum exper-
imental set-up for voltammetric determination of ATZ. During
optimization each parameter was changed while the others were
kept constant. It was found that the peak current of ATZ increased
as the modulation was rising from 20 to 120 mV accompanied by
the widening peak width (level of change was 10 mV). When the
amplitude was higher than 100 mV, the peak current became much
wider (minima before and after the peak maximum presented more
than 0.4 V). The variation of frequencies was studied in the range
of 10–100 Hz with level of change of 10 Hz. The peak current of
ATZ increased with frequency up to 100 Hz, above which it became
unstable as well as large current fluctuations were observed. By
fixing the frequency of 60 Hz, the effect of step potential was also

Table 3
Influence of potential interfering agents on the current response of ATZ.

Interfering agent Concentration (mM) Signal change (%)

2+ 2+ + +
Ca , Mg , K , Na 1 <0.5
Cl− , NO3 − , PO4 3− , SO4 2− , CO3 2− 1 <1.4
Hg2+ , Cu2+ , Bi3+ , Cr6+ , As3+ 1 +2.1
Fig. 3. CV voltammograms of 10 ␮M ATZ in BRBS at pH 3 on BDD electrode for series
Pb2+ , Cd2+ 0.8 +3.8
of scan rates from 0.015 to 0.150 V s−1 . The dependence between peak current and
Zn2+ 0.5 +6.4
square root of the scan rate appears in the inset.
298 L’. Švorc et al. / Sensors and Actuators B 181 (2013) 294–300

Table 4
Determination of ATZ in river waters spiked with ATZ (n = 6).

Sample Added (␮M) Proposed methoda (␮M) Recoveryb (%) Reference methoda (␮M)

S1 25 24 ± 2 96 23
S2 25 25 ± 3 100 24
S3 25 23 ± 2 92 24
a
Confidence interval calculated according [x ± tn − 1, ␣ SD/sqrt(n)]; t5; 0.05 = 2.0150.
b
Calculated as found concentration values divided by added ATZ concentration values multiply by hundred.

studied, because these two parameters define the scan rate. At step
potential greater than 5 mV, too few points were sampled, thus
influencing the repeatability of measurements. Table 1 shows the
range of studied SWV instrumental parameters, level of change and
the optimum values which were further used in calibration curve
construction.
3.2.2. Determination of ATZ
Under the optimized conditions, the applicability of SWV for
the determination of ATZ was examined by construction of cali-
bration curve by plotting the peak current against concentration
of ATZ in BRBS at pH 3 as depicted in Fig. 4. The analytical param-
eters are listed in Table 2. The low detection limit of 10 nM and
linear concentration range from 0.05 to 40 ␮M were acquired as
a consequence of high S/N ratio without any surface pretreat-
ment or modification. The repeatability of method was studied
by six replicate SWV measurements at the 10 ␮M ATZ concen-
tration under the same operating conditions over the short time
interval with relative standard deviation (RSD) of 2.9%. The low
RSD value revealed the good repeatability of method and con-
firmed the low adsorption of product of electrode reaction on BDD
electrode.
3.2.4. Application of the method to the river water samples spiked
with ATZ
The standard addition method was used for analysis of river
water samples spiked with ATZ (S1–S3) when the aliquots amount
of standard solution of ATZ was added for evaluation of the accuracy
and the practical applicability of proposed voltammetric method.
The preparation of river water samples spiked with ATZ is consis-
tently described in Section 2.4. The average results of six replicate
measurements expressed as confidence interval for 95% probabil-
ity obtained for determination in river waters spiked with ATZ
using the proposed and reference HPLC method are summarized
in Table 4. The satisfactory recovery values between 92 and 100%
were obtained for all samples. It indicated that there are no signifi-
cant interferences of matrix of the water samples and also that the
proposed method is accurate as well as suitable for quantification
of ATZ. By comparison of results, it can be concluded that the values
acquired by the proposed method well agree with those obtained
by reference HPLC method. Applying the paired t-test [39] to the
results obtained by both methods, the resulting t-value of 0.5 is
smaller than the critical one (4.30 for ˛ = 0.05), indicating that there
is no significant difference between these results at the confidence
interval for 95% probability.

3.2.3. Interference studies 3.2.5. Comparison with other electrochemical methods

Under the same experimental and SWV instrumental condi-
tions, the influence of potential interfering agents was investigated
by addition of each one to solution with fixed concentration of
10 ␮M ATZ. In this context, the particular agent was considered
to be serious interferent when it gave the signal change of ATZ
more than 5%. It is well known that ATZ may be chemically or bio-
logically degraded in the environment, but the influence of major
product of degradation process (2-hydroxyatrazine) has not been
studied. The results of influence of some ions are given in Table 3. It
is obvious that the peak current of ATZ was not significantly affected
by substantial 100-fold excess of more tested cations and anions
as confirmed by the values of signal change. Except bivalent zinc
which 50-fold excess overreached the value of ATZ signal change
of 5% because of close position of peak potentials of zinc and ATZ.
In spite of this fact we can conclude that the proposed method pro-
vided the sufficient selectivity in the voltammetric determination
of ATZ.
A comparison between the analytical performance of the
proposed method and reported electrochemical methods for deter-
mination of ATZ is given in Table 5. Generally, the methods using
highly toxic mercury electrodes are considered to be the most
sensitive for electrochemical determination of ATZ with lowest
detection limit [17,18,20]. The several papers focused on searching
the perspective and environmentally acceptable electrode surfaces
capable of reduction of ATZ with good sensitivity, repeatability
and low cost but without the increase of toxic waste produced
have been published [23–25]. In this context, the solid amalgam
electrodes often prolong the overall time of analytical procedure
because of the necessity of preparation of nontoxic amalgam [24].
It should be pointed out that the detection limit achieved in this
work is comparable than those obtained on mercury electrodes.
Moreover, BDD electrode with SWV technique fulfills the demands
of modern electroanalytical chemistry (rapidity, simplicity, sen-
sitivity, repeatability and low cost). It could also represent the

Table 5
Comparison of the proposed method with previously reported electrochemical methods for determination of ATZ.

Working electrode Supporting electrolyte Technique Peak potential (V vs. Ag/AgCl) Linear range (␮M) Detection limit (nM) Application References

HMDE BRBS, pH 2.0 SI-SWV −1.0 0.116–2.32 21 River water 17

HMDE BRBS, pH 1.9 SWV −0.94 0.046–1.2 9 River water 18
SMDE 1 M H2 SO4 DPV −0.91 – 74 Soil and water 20
MFE NH4 OAc–HCl AdSSWV −0.50 0.002–0.278 0.1 Soil and water 23
CuSAE 0.1 M Na2 SO4 SWV −0.98 – 14 Natural water 24
BIFE ABS, pH 4.5 AdSDPV −0.95 0.67–20 140 Natural water 25
BDDE BRBS, pH 3.0 SWV −1.1 0.05–40 10 River water This work

Abbreviations: HMDE hanging mercury drop electrode, SMDE static mercury drop electrode, MFE mercury film electrode, CuSAE copper solid amalgam electrode, BIFE bis-
muth film electrode, BDDE boron-doped diamond electrode, BRBS Britton–Robinson buffer solution, ABS acetate buffer solution, SI-SWV sequential injection-square wave
voltammetry, SWV square-wave voltammetry, DPV differential pulse voltammetry, AdSSWV adsorptive stripping square-wave voltammetry, AdSDPV adsorptive stripping
differential pulse voltammetry
 L’. Švorc et al. / Sensors and Actuators B 181 (2013) 294–300
nontoxic (green) alternative for the environmental monitoring of
trace amounts of triazine herbicides and other harmful organic
compounds.
4. Conclusions
BDD electrode was used for the first time in combination with
SWV technique to elaborate the novel, simple and cheap alterna-
tive analytical method for determination of ATZ. At optimized SWV
instrumental conditions (step potential of 5 mV, frequency of 60 Hz
and amplitude of 80 mV), the detection limit of 10 nM, the linear
concentration range from 0.05 to 40 ␮M and the good repeatability
(RSD = 2.9%) was estimated in BRBS at pH 3. The method is suffi-
ciently selective because the majority of possible interferents does
not influence the reduction peak of ATZ even in a 100-fold excess.
The proposed procedure was applied for analysis of river waters
spiked with ATZ without complex sample pretreatment with the
results in good agreement with those obtained by reference HPLC
method. By this study we would like to demonstrate that BDD may
be used as sensitive and environmentally acceptable (green) elec-
trode material for the environmental monitoring of pesticides and
can replace highly toxic mercury electrodes or complex and expen-
sive chromatographic methods.
Acknowledgements
This work was supported by the Grant Agency of the Slovak
Republic (grant No. 1/0051/13) and the Slovak Research and Devel-
opment Agency under the Contract No. APVV-0797-11.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2013.02.036.
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Biographies
Dr. L’ubomír Švorc belongs to the young scientist of less than 35 years at Slovak
University of Technology in Bratislava in Slovak Republic. In his young age, he is
the author and co-author of more than 30 scientific papers registered in CC. He has
engaged in research on structural study of potential drugs by X-ray structural anal-
ysis, chromatographic methods dealing with the analysis of organic pollutants in
non-fatty foods as well as study of degradation of biologically active compounds
in wastewaters using Fenton reaction for several years. Since 2009, his interest
is focused on the development and the use of new electrode materials based on
boron-doped diamond for solving the tasks of food, clinical and environmental trace
analysis. His scientific work is also associated with intensive education of students
in bachelor, semestral and diploma works.
Assoc. prof. Miroslav Rievaj is an experienced long-term university teacher. His
technical and pedagogical experiences are necessary in planning and accomplish-
ing the complex experiments, effective interpretation of the scientific results and
supervision of diploma and bachelor projects. He is author and co-author more than
40 scientific papers published journals registered in CC.
Prof. Dušan Bustin is a well-known personality of the (electro)analytical chemistry.
He has over 45 years of scientific experience some also from abroad universities. He
is author and co-author more than 100 scientific papers published journals regis-
tered in CC and 58 scientific papers published journals registered in CA.