Journal of Electroanalytical Chemistry 770 (2016) 613

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Journal of Electroanalytical Chemistry

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

Voltammetric behavior, quantitative determination, and corrosion

investigation of herbicide bromacil
Mariola Brycht a,1, Tue zmen b, Barbara Burnat a,1, Kinga Kaczmarska a, Andrzej Leniart a,1,
Mustafa Tatekin b, Esma Kl b, Sawomira Skrzypek a,
a
University of Lodz, Faculty of Chemistry, Department of Inorganic and Analytical Chemistry, Tamka 12, 91-403 Lodz, Poland
b
Ankara University, Faculty of Science, Department of Chemistry, Dgol street, 06100, Tandogan, Ankara, Turkey

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

Article history: A boron-doped diamond electrode (BDDE) was applied for a simple, and sensitive electroanalytical determina-
Received 13 October 2015 tion of a fungicide, bromacil (Bro), using differential-pulse voltammetry (DPV). For the rst time, the electro-
Received in revised form 15 February 2016 chemical oxidation of Bro using a BDDE at +1.65 V vs. an Ag/AgCl reference electrode in BrittonRobinson (B
Accepted 3 March 2016
R) buffer, pH 2.0 was investigated. To obtain the optimum experimental conditions, the effects of the pH, modu-
Available online 22 March 2016
lation amplitude, modulation time and step potential were studied. Under optimum conditions, the DP
Keywords:
voltammetric determination of Bro was performed in the concentration range of 5.00 1067.50
Bromacil 105 mol L1 (LOD = 1.26 106 mol L1, LOQ = 4.22 106 mol L1), and the validation of the method
Herbicide was carried out. The developed procedure was successfully applied to determine Bro in a spiked river water sam-
Boron-doped diamond electrode ple by the standard addition method. To achieve valuable information regarding the electrochemical oxidation
Voltammetric determination mechanism of the pesticide Bro on BDDE, the cyclic voltammetry (CV) technique was applied. Additionally, the
Corrosion inuence of Bro on the corrosion properties of stainless steel employed to produce agricultural tools was inves-
tigated by means of electrochemical methods, e.g. linear polarization close to the corrosion potential for corrosion
rate determination, and potentiodynamic anodic polarization to characterize the resistance to pitting corrosion.
Corrosion damage was characterized by means of optical microscopy.
2016 Elsevier B.V. All rights reserved.

1. Introduction
The development of new electrode materials is one of the current
trends in electrochemistry. Most of all, carbon materials have attracted
great interest as electrodes for their application in the area of electroan-
alytical chemistry. Some of them which have been investigated as work-
ing electrodes in voltammetry are carbon paste [14], glassy carbon [3,
57], screen-printed carbon [3,8,9], pyrolytic graphite electrodes [10,
11], etc. Recently, a boron-doped diamond electrode (BDDE), as a rela-
tively new-generation environmentally friendly electrode, represents
a prospective electrode material which exhibits advantageous electro-
chemical properties, such as a very low and stable background current,
a wide working potential window, and high current density [12,13].
Due to its excellent physical and chemical robustness [14], hardness,
high thermal conductivity, and chemical inertness of the BDDE [15], it
is a widely used electrode for the voltammetric analysis of various bio-
logically active compounds [6,1627].
At the moment, pesticides play an important role in the production
and development of many crops. Although there are benets in the
Corresponding author.
E-mail address: skrzypek@uni.lodz.pl (S. Skrzypek).
1
ISE member.
use of pesticides, there have also been many problems associated with
their application in the environment. Unfortunately, the pesticides do
not always stay on target and they are mobile in the environment, can
drift, cause harm even if they are applied properly. Due to the harmful
effects of pesticides on the environment and living organisms it is im-
portant to develop sensitive analytical methods for their determination.
By far, chromatographic methods are the most commonly used for the de-
tection of pesticide residues. Nevertheless, these methods are technically
demanding, time consuming, and relatively expensive. Nowadays, elec-
trochemical methods represent an alternative to the aforementioned
methods, particularly due their satisfactory sensitivity, wide linear con-
centration range, operation simplicity, low cost of instrumentation, possi-
bility of miniaturization, relatively short analysis time, and suitability for
real-time detection [2830].
It is also worth noting that the use of pesticides in agriculture can be
damaging for the metal parts of agricultural tools and equipment due to
the fact that they may be highly corrosive [31]. Therefore, it is very im-
portant to investigate the effect of pesticides on the corrosion properties
of metal substrates. The literature sources report the corrosivity of some
pesticides when they are in contact with aluminum, brass, steel [31],
and copper [32]. Moreover, corrosion resistance against uniform and
pitting corrosion may be determined under laboratory conditions. There-
fore, electrochemical methods such as linear polarization resistance and

http://dx.doi.org/10.1016/j.jelechem.2016.03.028
1572-6657/ 2016 Elsevier B.V. All rights reserved.
 M. Brycht et al. / Journal of Electroanalytical Chemistry 770 (2016) 613
potentiodynamic anodic polarization [33,34] may be applied for the cor-
rosion tests.
Bromacil (Bro 5-bromo-3-sec-butyl-6-methyluracil, CAS Reg. No.
314-40-9, Fig. 1) is one of a group of compounds called substituted ura-
cils. Bro is a systemic, broad-spectrum and non-selective herbicide used
for the control of annual and perennial weeds and brush [35]. The mode
of action of Bro is to enter the plant through the root zone and move
throughout the plant, inhibiting photosynthesis [36]. Bro was rst regis-
tered as a pesticide in the U.S. in 1961, and since its discovery it has been
used in a variety of agricultural and non-agricultural situations [35]. Bro
is found in the list of priority pollutants of the US Environmental Protec-
tion Agency (US EPA) [36], and the EPA classies Bro as a Group C pos-
sible human carcinogen based on increases in the incidence of liver
tumors in male mice, positive trends in thyroid tumors in male rats,
and, to a lesser extent, its structural activity relationship to similar com-
pounds [36].
To date, few analytical methods have been established for the deter-
mination of Bro, mainly using chromatographic methods such as HPLC
[37,38], LC [39] and GC [40]. Moreover, several multiresidue pesticide
analysis methods have been developed and reported [4144]. To the
best of the authors' knowledge, no information about the electrochem-
ical behavior of Bro has so far been reported in the literature. Therefore,
for the rst time, this paper describes an electrochemical approach to
bromacil.
The aim of this work was to develop a procedure for the determina-
tion of Bro on a BDDE and methods for its DPV determination in spiked
river water. Moreover, to obtain valuable information about the
electrooxidation mechanism of Bro at BDDE, the cyclic voltammetry
(CV) technique was applied. Furthermore, the effect of Bro on the corro-
sion properties of stainless steel used to produce agricultural tools was
studied using several electrochemical methods (linear polarization
close to the corrosion potential for corrosion rate determination, and
potentiodynamic anodic polarization to characterize the resistance to
pitting corrosion). The characterization of corrosion damage was also
performed using optical microscopy.
2. Experimental
2.1. Electrodes, electrochemical cell and instrumentation
Differential-pulse (DPV) and cyclic voltammetry (CV) were per-
formed with a Autolab type II potentiostat-galvanostat (EcoChemie,
Autolab B.V., Utrecht, the Netherlands) controlled by GPES software
(General Purpose Electrochemical System, version 4.9) in combination
with an M164 electrode stand (MTM Anko Instruments, Cracow,
Poland). All measurements were provided in a threeelectrode setup,
where: silver/silver chloride electrode/potassium chloride (Ag/AgCl,
3.0 mol L1 KCl, Mineral, Poland) and platinum wire (99.99%, Mennica
Pastwowa S.A., Warsaw, Poland) served as reference and counter elec-
trodes, respectively. A commercially available boron-doped diamond
Fig. 1. Structure of Bro.
7
electrode (BDDE) with an inner disk diameter of 3.0 mm (geometric
area 7.1 mm2, electrical resistivity of 0.075 cm, B/C ratio during the
deposition step of 1000 ppm, declared by Windsor Scientic Ltd.,
United Kingdom as the producer) was used as a working electrode.
The pH measurements were carried out on an Orion Star pH meter
(Model A111, Thermo Scientic, the Netherlands) with a pH electrode
(type Polilyte Lab, Hamilton, Switzerland).
Corrosion studies based on electrochemical measurements were
carried out using an Autolab PGSTAT 30 potentiostat-galvanostat
(EcoChemie Autolab B.V., Utrecht, the Netherlands) with GPES software
(version 4.9). In corrosion tests a conventional three-electrode cell as-
sembly was used. AISI Type 316L stainless steel (Medgal, Poland) was
used as a working electrode (an exposed area of 0.64 cm2), a saturated
calomel electrode (SCE, Eurosensor, Gliwice, Poland) was applied as a
reference electrode, and platinum foil (99.9%, Mennica Pastwowa
S.A., Warsaw, Poland) was used as a counter electrode. An MMT
800BT optical microscope (mikroLAB, Lublin, Poland) was used for the
characterization of corrosion damage.
2.2. Reagents and solutions
Bro (CAS No. 314-40-9, PESTANAL, Fluka, Poland) was of 98.5% pu-
rity. A fresh Bro stock solution (1.0 103 mol L1) was prepared by
dissolving an exact weight of the pure substance in a wateracetone
mixture (9:1, v/v), and the standard solution was stored in a glass
ask in a refrigerator. The changes in consistency and stability of the
stock solution of Bro were not observed during a few weeks. Orthophos-
phoric acid, acetic acid, boric acid, sodium hydroxide, sulfuric acid, nitric
acid, and acetone (all p.a. purity) were purchased from POCh SA (Gliwi-
ce, Poland). BrittonRobinson buffer (BR) solutions were prepared in
the usual way, i.e. by mixing the same concentrations (0.04 mol L1)
of H3PO4, H3BO3 and CH3COOH in water and adjusting to the desired
pH value with the appropriate amount of sodium hydroxide solution
(0.20 mol L1), covering the pH range of 2.011.0.
Sodium chloride (analytical reagent grade, POCh SA, Gliwice, Poland)
was used as the corroding medium. Corrosion tests were carried out in a
3.5% solution of NaCl prepared in a wateracetone mixture (1:1, v/v), both
with and without the addition of Bro (1.0 103 mol L1). The solutions
were used without further deoxygenation.
All solutions were prepared in triply distilled water. All electrochem-
ical measurements were carried out at laboratory temperature.
2.3. Measurements procedure
2.3.1. Voltammetric procedures
BDDE was activated at the beginning of each working day in a stirred
0.10 mol L1 sulfuric acid solution by applying a potential of +2.4 V (vs.
Ag/AgCl, 3.0 mol L1 KCl) for 30 s.
Optimized DPV parameters were as follows: step potential of 10 mV,
and modulation amplitude of 90 mV. In CV, the scan rate in the range
from 10 mV s1 to 500 mV s 1, and the potential range from 0 V to
+2.0 V were used.
The general voltammetric procedure to obtain the blank signal was
as follows: the supporting electrolyte solutions were prepared in
10 mL volumetric asks by measuring 1 mL of wateracetone mixture
(9:1, v/v) and lling up to the mark with BR buffer of appropriate pH.
The solutions with pesticides for measurements were prepared in
10 mL volumetric asks by measuring the proper volume of the Bro
stock solution and lling up to the mark with BR buffer of the required
pH.
The measured signals were evaluated by subtracting the blank
solution.
2.3.2. Corrosion procedures
The corrosion tests were carried out on AISI 316L stainless steel sam-
ples in the form of disks with a diameter of 16 mm and a thickness of
8 M. Brycht et al. / Journal of Electroanalytical Chemistry 770 (2016) 613

5 mm. Prior to corrosion measurements the surfaces of each sample
were ground on SiC abrasive paper (320, 500, and 1000 grits), cleaned
in water in an ultrasonic bath for 10 min, rinsed with ethanol and
dried with argon.
For the determination of the corrosion properties of AISI 316L stain-
less steel in Bro-containing sodium chloride solutions the following
electrochemical measurements were performed: (1) the measurement
of corrosion potential (Ecor) in an open circuit (OCP) over 2000 s; (2) the
measurement of polarization resistance (Rp) according to the Stern
Geary method in the scanning range of Ecor 20 mV with a scan rate
of 0.3 mV s1; and (3) the measurement of the potentiodynamic char-
acteristic in the scanning potential range from Ecor 0.2 V up to +1.5 V
with a scan rate of 1.0 mV s1. Next, the surfaces of samples were exam-
ined using an optical microscope for the characterization of corrosion
damage. Four samples were used for every corrosion test. The results
presented in this paper are averaged values with condence intervals
(p = 95%).
2.3.3. Preparation of model sample river water
The sample of river water was collected from the Mroga River
(Rochna, Poland), and was analyzed without further pretreatment or
purication.
To study the possible interferences caused by river water, 9 mL of B
R buffer, pH 2.0 and 1 mL of the river water were placed in a
voltammetric cell, and the DPV curve of the blank was recorded.
A stock solution of Bro (1 mL) was transferred to a 10 mL volumetric
ask and lled up to the mark with the river water. To record the DP
voltammogram of the spiked river water sample, 1 mL of the above
solution was poured into the voltammetric cell containing 9 mL of B
R buffer, pH 2.0. Consecutive additions of Bro were added to the
voltammetric cell using a micropipette (the concentrations were
9.90 10 6 mol L 1, 1.96 105 mol L1, and 2.91
105 mol L1). The voltammograms were recorded after each addition
(four replicate determinations) using the standard addition method.
3. Results and discussion
3.1. Cyclic voltammetric studies of Bro at BDDE
In the present paper, the CV technique was used to achieve valuable
information regarding the electrochemical oxidation mechanism of the
pesticide Bro at BDDE. Recorded cyclic voltammograms of Bro at differ-
ent scan rates () from 10 mV s1 to 500 mV s1 in the potential range
from 0 V to +2.0 V with 0 V as starting potential at a Bro concentration
level of 1.0 104 mol L1 in BR buffer pH 2.0 (Fig. 2A) indicated the
presence of two peaks in the anodic run (Ep1 = + 1.65 V and Ep2 =
+1.9 V). In the backward scan of the same voltammograms no peaks
was observed, suggesting the irreversible two-step Bro oxidation at
BDDE.
It is also worth noting that as the scan rate was increased from
10 mV s1 to 500 mV s1, the anodic peak potential shifted towards
more positive values (Fig. 3D) from +1.66 V to +1.78 V, and this be-
havior conrms the irreversibility of the oxidation process.
In the present paper, the dependence of the peak intensity (Ip) of Bro
upon the scan rate () was carried out to assess whether the process on
BDDE is diffusion- or adsorption-controlled. The obtained results

Fig. 2. (A) Cyclic voltammograms of 1.0 104 mol L1 Bro in dependence on the scan rate () recorded on BDDE in BR buffer, pH 2.0; scan rate (): (a) 10, (b) 25, (c) 50, (d) 75, (e) 100,
(f) 200, (g) 300, and (h) 500 mV s1. The inset shows the cyclic voltammogram of Bro recorded in the scan rate = 0.05 V s1; (B) The linear dependence of the peak current (Ip) of Bro on
the square root of the potential scan rate (1/2); (C) The linear dependence of the logarithm of the peak current (log Ip) of Bro on the logarithm of the potential scan rate (log ); (D) The
dependence of the peak potential (Ep) of Bro on the potential scan rate ().
 M. Brycht et al. / Journal of Electroanalytical Chemistry 770 (2016) 613 9

Fig. 3. (A) DP voltammograms of Bro (1.0 104 mol L1) on BDDE in BR buffers, pH 2.011.0; (B) Corresponding dependences of the DPV peak currents (Ip) (, left y axis) and peak
potentials (Ep) (, right y axis) on pH.

showed that the anodic peak current (Ip) at Ep1 = +1.65 V is directly NH group. However, it should be stressed that the investigation of
proportional to the square of the scan rate (1/2) (Fig. 2B), and the rela- the oxidation structure of Bro is beyond the scope of this study.
tionship can be described by the following equation:
 1=2  
Ip A 0:11791=2 mV s1 0:0092 R2 0:9924 3.2. Optimization of experimental parameters: inuence of pH and DP
parameters on the voltammetric behavior of Bro

Moreover, the relationship between the logarithm of the peak cur-

In order to acquire knowledge about the redox behavior of Bro and
rent (log Ip) and the logarithm of the scan rate (log ) was analyzed
to nd optimal experimental conditions for its voltammetric determina-
(Fig. 3C), and gave a slope of 0.4793, close to the theoretical value of
tion, extensive studies were performed. A study of the robustness of an
0.5, which is expected for an ideal reaction of solution species [30].
electrochemical method should begin with careful selection of the ex-
Such dependence indicated that the oxidation of Bro was indeed domi-
perimental variables that are crucial to the electroanalytical method. It
nated by diffusion-controlled process [30]. The obtained results demon-
was found that the voltammetric behavior of Bro at the BDDE depends
strated that the electrode process is controlled by diffusion, and this fact
on several factors, such as pH and DPV parameters.
is common for the BDDE surface in the determination of organic com-
It is well known that pH is one of the variables which commonly and
pounds due to its low adsorption properties [12]. The aforementioned
strongly inuence the shapes of voltammograms, and therefore it is
relationship may be described by the following equation:
very important to investigate the effect of pH on electrochemical sys-
    tems. As a preliminary study, the effect of BrittonRobinson buffer (B
log Ip A 0:4793 log mV s1 0:8885 R2 0:9946 R) solution as a supporting electrolyte over a pH range from 2.0 to
11.0 was tested using DPV in the anodic region for suitability in the de-
The applied CV and DPV techniques show that Bro gives oxidation termination of Bro (1.0 104 mol L1) using BDDE. The obtained re-
signals at high positive potentials which refer to its challenging oxida- sults, graphically depicted in Fig. 3A, conrm the oxidizability of Bro in
tion [45]. It is also important to note that Bro (Fig. 1) is one of a group the whole tested pH range of the BR buffer. Moreover, it was found
of compounds called substituted uracils. Based on the literature [45], that Bro provided two peaks at very positive potentials in BR buffers.
the results obtained for other uracil derivatives show that a higher However, a better dened and high oxidation peak was obtained at
value of negative charge is present on nitrogen as compared to oxygen less positive potentials, and therefore the rst peak was used for analyt-
and carbon atoms, and therefore nitrogen is responsible for the oxida- ical purposes.
tion in the uracils (oxidizable nitrogen). In the chemical structure of
Bro, two nitrogen atoms are present. Nevertheless, a non-substituted
Table 1
atom could be more easily oxidized. Presumably, the two peaks of Bro Parameters of the calibration straight lines for the determinations of Bro by DPV at BDDE in
are attributable to the existence of keto and enol tautomeric forms BR buffer, pH 2.0.
existing in equilibrium. Moreover, it can be assumed that with the de-
Linear concentration range (LDR) [mol L1] 5.0075.00
crease in pH values, the enolic form predominates due to the facile
Number of measurements (n) 5
oxidation of the carbonyl group in the acidic medium [45]. It is also im- Slope (b) [A L mol1] 0.0124
portant to note that based on previous studies [46], the mass spectra Standard error of slope (SEb)a 6.63 105
were identied using the LCMS technique, and fragment ions obtained Intercept (a) [A] 0.0049
Standard error of intercept (SEa)a 2.21 103
in positive and negative ionization modes were interpreted in order to
Coefcient of determination (R2) 0.9994
obtain information on the degradation products of Bro, suggesting the Limit of detection (LOD) [mol L1]b 1.27
proposed oxidation mechanisms. Limit of quantication (LOQ) [mol L1]c 4.22
Considering the above results, it can be suggested that the a
SE = SD/n1/2.
voltammetric response obtained at BDDE in the presence of Bro under b
LOD = 3 SD/b.
acidic conditions (BR buffer, pH 2.0) is caused by the oxidation of the c
LOQ = 10 SD/b.
10 M. Brycht et al. / Journal of Electroanalytical Chemistry 770 (2016) 613
Fig. 4. DP voltammograms of Bro measured on BDDE in BR buffer, pH 2.0. The inset shows
the corresponding calibration graph; (a) 2.50 106 mol L1, (b) 5.00 106 mol L1,
(c) 7.50 106 mol L1, (d) 1.00 105 mol L1, (e) 2.50 105 mol L1,
(f) 3.50 105 mol L1, (g) 5.00 105 mol L1, and (h) 6.25 105 mol L1.
Background measurements have been subtracted and normalized. The error bars are
constructed as condence intervals (t(p = 95%, n = 5) = 2.78.).
As can be seen from Fig. 3B, a large dependence of the signal heights
(Ip) and their potentials (Ep) on pH was observed. Furthermore, in all
media the signal is positioned relatively closely to the onset of the
supporting electrolyte, which inuences its height. Within the pH
range of 2.0 to 9.0, the peak intensities (Ip) decrease until attaining a
minimum at pH 9.0 and then slowly increase (Fig. 3B). Bearing in
mind the fact [47] that the morphological changes of BDDE surface
could be seen in aqueous alkaline solutions, and long-lasting use of
BDDE in strongly basic media could result in degradation of the surface
due to oxidation of the diamond layer, measurements in pH higher than
10 should be avoided. The highest signal with satisfactory repeatability
was obtained in BR buffer at pH 2.0. Other acidic unbuffered media
were also tested, although the utilization of nitric acid and sulfuric
acid was inconvenient due to less sensitive and reproducible current re-
sponses. Due to the fact that the optimum results in terms of the highest
analytical signal were observed in BR buffer, pH 2.0, this media was
used for further analytical studies.
Moreover, the increase in pH produced a negative shift of the oxida-
tion potential from +1.67 V to +1.47 V (Fig. 3B), which indicated the
existence of a protonation reaction coupled with the Bro oxidation pro-
cess. Presumably, the negatively charged non-substituted nitrogen,
which is probably responsible for the oxidation in Bro, is attracted to
the positively charged electrode which results to ca. 0.2 V shift of oxida-
tion potential. Moreover, this shift can also be explained by the prelim-
inary protonation of nitrogen leading to the decrease of electron density
on nitrogen atom, resulting in easier electron acceptance at low pHs.
The evolution of Ep with pH shows two almost linear segments
(Fig. 3B). The peak potentials shift towards less positive values (from
+1.67 V to +1.61 V) with the slope of 28.3 mV/pH in the pH range
2.08.0. At pH values higher than 8.0, the peak potentials shift signi-
cantly towards less positive values (+ 1.5 V) and remain constant.
This change can be associated with the acidic dissociation constant
pKa value of Bro (theoretical value of 9.30) [48]. Moreover, the pH inde-
pendent zone above pH 8.0 means that there are no proton transfer
Table 2
Analytical results of Bro determination in the spiked river water obtained by the proposed DPV procedure (n = 4).
Sample Added Founda [mol L1]
[mol L1]
Mroga River 10.00 10.41 0.62
a
Mean value condence interval, t(p = 95%, n = 4) = 3.18.
steps before the electron transfer rate-determining step. Since no disso-
ciation occurs before the electron transfer determining step, the oxida-
tion potential remains pH-independent. At pH values lower than pKa
(pH b pKa), the conjugate base must be formed by rapid dissociation
of the protonated form.
Moreover, to establish the optimum conditions for the determina-
tion of Bro using DPV on BDDE, the inuence of the DP parameters,
such as modulation amplitude (EDP), modulation time (tDP) and step po-
tential (E), was studied. During adjustment of the above-mentioned
parameters, each parameter was changed, while the others were kept
constant. The effect of the DP modulation amplitude (EDP) in the range
of 5100 mV on the Bro peak current with a xed modulation time of
50 ms was studied. In the studied range the peak heights increased
with rising EDP. Nevertheless, the best-shaped signal with sufcient cur-
rent response was obtained at a modulation amplitude of 90 mV. The in-
uence of the modulation time (tDP) of Bro was investigated in the range
from 0 s to 100 ms. It was found that the analytical signal of Bro at tDP
higher than 80 ms caused a decrease in the current response. Hence,
the highest peak was observed when a modulation time of 70 ms was
applied. The inuence of the step potential (E) was studied in the
range between 2 and 50 mV. The peak current increased with increasing
E, although step potential levels higher than 10 mV caused a distortion
in peak shape. The best results were obtained for E of 10 mV. There-
fore, the modulation amplitude of 90 mV, the modulation time of
70 ms, and step potential of 10 mV were used in further analytical
studies.
3.3. Analytical performance determination of Bro by the DPV technique
To obtain a calibration curve, DPV measurements were performed
under the optimal conditions described in Section 3.2, and the proposed
method was validated. The validation parameters such as linearity and
range, sensitivity, limit of detection (LOD), limit of quantication (LOQ),
precision (repeatability), and accuracy (recovery), were estimated.
The calibration curve was obtained by plotting the peak current (Ip)
against the increasing Bro concentration (cBro). The parameters of cali-
bration curves for Bro obtained using DPV are summarized in Table 1,
and corresponding DP voltammograms are presented in Fig. 4. The oxi-
dation peak increases linearly (the inset of Fig. 4) in the linear dynamic
range (LDR) of 5.00 106 mol L1 to 7.50 105 mol L1, and the re-
lationship can be described by the following equation:
   
Ip A 0:0124 c mol L
1
0:0049 R2 0:9994
The limit of detection (LOD = 1.27 10 6 mol L 1) and the limit
of quantication (LOQ = 4.22 10 6 mol L 1) of Bro were calculat-
ed from the calibration curve as follows: LOD = 3 SD/b and LOQ = 10
SD/b; where SD is the standard deviation, and SDs were calculated for
the intercept (a) (ve runs), and b stands for the slope (b) of the cal-
ibration graphs [4951]. The precision (repeatability) of the mea-
surements was tested by ve repeated scans (n = 5) at each
studied Bro concentration. In the concentration range of 5.00
10 6 mol L 17.50 10 5 mol L 1, the relative standard deviation
(RSD) of the DP peak current changed from 0.6% to 5.6%. In order to
check the correctness of the method, the precision and accuracy of
the method were also calculated for the different concentrations in
the linear ranges (RSD = 0.9% 5.5%; Recovery = 95.5% 101.7%).
Precision RSD [%] Average recovery [%] Bias [%]
3.8 104.1 4.09
 M. Brycht et al. / Journal of Electroanalytical Chemistry 770 (2016) 613
Fig. 5. DP voltammograms of Bro determination in the spiked Mroga River water samples
using the standard addition method; (1) river water sample spiked with Bro, (2) as
(1) + 9.90 106 mol L1; (3) as (1) + 1.96 105 mol L1; (4) as
(1) + 2.91 105 mol L1. Background measurements have been subtracted and
normalized. The error bars are constructed as condence intervals (t(p = 95%, n = 4) =
3.18.).
Hence, the obtained detection limit is relatively low (in the
10 6 mol L 1 concentration range), conrming the sensitivity of
the proposed method.
3.4. Application of the proposed DPV method for analysis of the model
sample river water
The developed DPV procedure was successfully applied to deter-
mine Bro in the spiked Mroga River water samples, prepared as de-
scribed in Section 2.3.3. It was stated that no interferences were
observed from the river water components. Four replicate determina-
tions were performed with the standard addition method in order to
perform the applicability of the procedure, and the RSD showed high re-
producibility of determination. The average of the results is shown in
Table 2. The obtained results indicate that the proposed procedure
using BDDE is feasible for the determination of Bro in river water sam-
ples. An example of DP voltammograms for the determination of Bro
in the Mroga River water samples, and a corresponding standard addi-
tion plot are shown in Fig. 5.
3.5. Corrosion tests
The corrosion studies were carried out in 3.5% NaCl solution contain-
ing Bro as the corrosion-inducing agent. The results of non-destructive
corrosion measurements performed close to open circuit potential are
summarized in Table 3. This table contains the values of corrosion po-
tential (Ecor), polarization resistance (Rp), corrosion current density
(icor), and corrosion rate (CR) parameters describing the corrosive
properties of the investigated steel samples in corrosion medium, both
with and without the addition of Bro. The values of the corrosion rate
were calculated based on the determined values of polarization resis-
tance, according to the standard ASTM G 102-89 [52], with the
Table 3
Values of corrosion parameters of AISI 316L steel in 3.5% NaCl solution without and with the addition of Bro (1.0 103 mol L1).
Solution Ecor vs. SCEa/V Rpa/M cm2
NaCl 0.1409 0.0015 0.449 0.050
NaCl + Bro 0.096 0.040 0.526 0.037
a
Mean value condence interval, t(p = 95%, n = 4) = 3.18.
11
Fig. 6. The effect of 1.0 103 mol L1 Bro on the potentiodynamic polarization curves for
AISI 316L in 3.5% NaCl solution (scan rate of 1.0 mV s1).
assumption that the corrosion processes at Ecor potential occur as a uni-
form type of corrosion.
The obtained results shown that Bro has a benecial effect on the
corrosion resistance of AISI 316L stainless steel in NaCl solution. The ad-
dition of Bro shifts the value of the corrosion potential to more positive
potential value. Moreover, the higher values of polarization resistance,
as well as lower values of corrosion current density and corrosion rate,
indicate the better corrosion resistance of the investigated steel in the
Bro-containing solution.
The effect of the herbicide Bro on the pitting corrosion resistance of
AISI 316L steel in chloride-containing solution was investigated by re-
cording of anodic polarization characteristics. The potentiodynamic
characteristics gathered in a wide range of anodic polarization, and
the values of the pitting potential (Epit) obtained from these characteris-
tics are shown in Fig. 6. The pitting potential was taken as the potential
value where an abrupt increase in the anodic current density was ob-
served. As can be seen in Fig. 6, the addition of Bro to the corrosion me-
dium changes the pitting resistance of AISI 316L steel. In sodium
chloride solution without Bro (pH 6.4) the investigated steel has a low
pitting potential value of 0.40 V, indicating the relatively weak resis-
tance of this steel to pitting corrosion in an aggressive environment of
chloride ions. Whereas, in Bro-containing sodium chloride solution the
steel shows a wider passive range and a higher Epit value of 0.96 V.
Some prepitting may also be observed in the range of 0.60.9 V, but
the prepits undergo deactivation very quickly. Another benecial effect
of Bro is the lower value of the anodic current in the passive range when
compared to the pure NaCl solution. As a result of anodic polarization in
both solutions, the pits were formed on the steel surface.
Optical microscopic images of representative pits formed in NaCl so-
lution without and with the addition of Bro are presented in Fig. 7. In the
case of the sodium chloride solution without the addition of Bro, a few
randomly distributed large pits (approx. 500 m in diameter) were
observed. Conversely, the corrosion damage occurred in the Bro-
containing sodium chloride solution was signicantly smaller. The
resulting pits were smaller in size, and of a different morphology.
They were arranged only on the periphery of the active surface (bound-
ed by the size and shape of the silicone gasket). This smaller corrosion
icora/Acm2 CRa/mm year1
0.0594 0.0071 (6.25 0.75) 104
0.0512 0.0059 (5.39 0.59) 104
12 M. Brycht et al. / Journal of Electroanalytical Chemistry 770 (2016) 613
Fig. 7. Optical microscope images (magnitude of 100) of pits formed on the AISI 316L surface due to anodic polarization.
damage may be a result of the better passivity of steel due to the forma-
tion of a more compact passive layer in the presence of Bro.
Based on the results of the presented potentiodynamic characteristics
and microscopic analysis, it can be concluded that in this case Bro acts as a
corrosion inhibitor and improves the resistance of the investigated steel
to pitting corrosion. Similar corrosion inhibition of other uracils (Bro
belongs to the group of uracils) has been reported in the literature
[5355]. It was proven that uracils exhibit inhibitive properties against
steel, zinc and lead in acidic solutions [53]. According to these researchers,
the efciency is attributed mainly to the presence of N and O atoms as ac-
tive centers for adsorption of the organic molecule onto the metallic
surfaces.
4. Conclusions
A novel and alternative electroanalytical method for the determina-
tion of Bro at BDDE was developed, and the advantages of this
voltammetric methodology, such as simplicity, cheapness, and rapidity
were demonstrated by successful application in the spiked river water
samples without any sample preparation. The oxidation of Bro at very
positive potentials seems to eliminate a possible interferences. The ob-
tained results showed that BDDE turned out to be a useful tool for the
detection and quantication of Bro in river water samples. Furthermore,
the results obtained using cyclic voltammetric technique show that the
BDD electrode mechanism is an irreversible process controlled by the
diffusion of Bro. The investigation of the effect of pesticides on the cor-
rosion properties of metal substrates carried out using electrochemical
methods show that Bro has a benecial effect on the corrosion resis-
tance of stainless steel used to produce agricultural tools. It was also
stated that Bro improves resistance against the uniform and pitting cor-
rosion of AISI 316L stainless steel in 3.5% NaCl solution, and in this case
Bro acts as a corrosion inhibitor for steel.
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