Electrochimica Acta xxx (2015) 421–429

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

Sensitive voltammetric method for rapid determination of pyridine

herbicide triclopyr on bare boron-doped diamond electrode
Lenka Janíková-Bandžuchová a, *, Renáta Šelešovská a , Karolina Schwarzová-Pecková b ,
Jaromíra Chýlkov a
a
University of Pardubice, Faculty of Chemical Technology, Institute of Environmental and Chemical Engineering, Studentská 573, CZ-53210, Pardubice, Czech
Republic
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-12843, Prague 2, Czech Republic

A R T I C L E I N F O A B S T R A C T

Article history: Voltammetric method for the determination of a pyridine herbicide triclopyr (3,5,6-trichloro-2-
Received 5 September 2014 pyridyloxyacetic acid) is presented for the first time using bare boron-doped diamond electrode.
Received in revised form 10 December 2014 Triclopyr provides one well-developed, pH-independent oxidation signal at ca. +1.9 V (vs. AgjAgCljKCl
Accepted 10 December 2014
(sat.)) contrary to structurally related clopyralid, which is not oxidizable at the working electrode.
Available online xxx
Britton–Robinson buffer (pH 2.0) was chosen as optimal electrolyte for determination of triclopyr using
square wave and differential pulse voltammetry. The latter method provided slightly better detection
Keyword:
limit of 0.82 mmol L1 and linearity in the concentration range 1.0–108.8 mmol L1. Applicability of the
Triclopyr
Clopyralid
proposed method was verified by analysis of pesticide preparation, spiked water and urine with excellent
Herbicide results.
Boron-doped diamond electrode ã 2014 Published by Elsevier Ltd.
Voltammetry,

1. Introduction of TCP [8,9]. Recently, derivative spectrophotometric method was

Triclopyr (TCP, 3,5,6-trichloro-2-pyridyloxyacetic acid) is a
selective, systemic, pyridine herbicide, which is mostly employed
for a control of woody and herbaceous broadleaf plants along right-
of-ways, in forests, and in parks. It has little or none effect on
grasses. It acts as a synthetic growth hormone, which causes
uncontrolled plant growth in the susceptible plants [1,2]. TCP is
water soluble and non-persistent in surface waters due to the
sunlight degradation. It has limited mobility and moderate
capability of the accumulation in soils and constitutes a slight
risk of a groundwater contamination. The average half-life of TCP in
soils is about 30 days [1–3]. Generally, TCP has low toxicity to
mammals and other wildlife but its derivatives or metabolites are
moderately toxic to aquatic fauna [2,3].
Various analytical methods have been developed for sensitive
and precise determination of TCP. The most commonly used one is
gas chromatography (GC) with an electron capture [4] and mass
spectrometric [5–7] detector. High performance liquid chroma-
tography (HPLC) with various preconcentration techniques in
combination with UV detector was also applied for determination
* Corresponding author. Tel.: +420 466 038 080.
E-mail address: lenka.janikova@upce.cz (L. Janíková-Bandžuchová).
utilized as a tool for determination of TCP and other member of
pyridine herbicide family (picloram) in a mixture [10]. Possibilities
of TCP analysis using immunoassay methods were investigated as
well [11,12].
The electrochemical methods have many advantages, especially
the low costs of equipment, undemanding samples treatment, and
particularly fast and sensitive performance of analysis and thus
they can be found as a suitable alternative option to the above
mentioned analytical techniques [13]. On the basis of the literature
survey, any described electrochemical method was not found for
detection of TCP but electrochemical reduction of structurally
related compounds to TCP like picolinic acid [14], 6-chloropicolinic
acid [15], clopyralid [16,17], 3,5,6-trichloro-4-methyl-pyridine-2-
carboxylic acid [18], and picloram, e.g. in [17,19,20], has been
widely investigated using working electrodes made of liquid
mercury in various construction [14–17,19,20] or glassy carbon
electrode [18].
Boron-doped diamond (BDD) is one of the relatively novel and
perspective electrode materials, which has been firstly described
in the eighties [21] and has been widely investigated in
electroanalysis in the last twenty years for its superior electro-
chemical properties such as a low and stable background over the
wide potential range, high thermal conductivity, and chemical
stability [22–24]. Application of this electrode material in

http://dx.doi.org/10.1016/j.electacta.2014.12.064
0013-4686/ ã 2014 Published by Elsevier Ltd.
422 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429
electroanalysis of organic compounds has been reviewed e.g. in
[22–27]. The newer and perspective trends include miniaturization
of BDD sensors for their utilization in in vivo/in vitro analysis or for
detection in capillary electrophoresis or micro total analytical
systems [24,28,29], utilization of adsorptive techniques in the
presence of surfactant interacting with organic analytes, which
increases the selectivity and sensitivity of proposed methods
[30,31], or modification of BDD surfaces and their utilizations in
construction of BDD-based sensors (for details, see [32,33]).
Promising strategies include e.g. amination or carboxylation of
BDD surface to bond various receptor biomolecules [26,33,34], or
covering of BDD thin films by molecularly imprinted conducting
polymers such as polypyrrole [35,36].
At bare BDD electrodes, advantageous are primarily methods
based on electrochemical oxidation due to extended potential
window in aqueous or mixed aqueous-acetonitrile media. This is
given by the high overpotential of oxygen evolution reaction,
initiated by the one electron transfer from water under formation
of hydroxyl radicals generated in the region of water decomposi-
tion as the first and rate determining step [22,26] (Eq. (1)):
H2O (BDD) ! HO(BDD) + H+ + e
Pesticides and their metabolites represent one group of
compounds studied by means of bare BDD electrodes as
demonstrated for carbamate pesticides [37,38], chloromethylphe-
noxy herbicides [39], fungicides kresoxim-methyl [40] and
dimethomorph [41], triazine herbicide atrazine [42], insecticide
methyl parathion and its degradation product 4-nitrophenol [43–
47], insecticide mancozeb [48], and herbicide paraquat [49]. Our
research group investigated the voltammetric behavior of pyridine
herbicide picloram (PCR) on two types of BDD electrode–
commercial [50–52] and self-assembled sensor [51,53]. The
proposed reliable and sensitive methods were applied for analysis
of model and spiked samples of natural and biological materials
[50–53].
On the basis of the literature survey, any paper dealing with
electrochemical determination of TCP using reductive processes or
studies on its electrooxidation was not found. Thus, for the first
time in this paper an electroanalytical approach using oxidation at
bare BDD electrode, as a green and sensitive sensor is presented.
The mechanism of electrooxidation has been proposed based on
cyclic voltammetric experiments. Further, the used media and
working parameters of pulse voltammetric techniques (differential
pulse voltammetry (DPV) and square wave voltammetry (SWV))
have been optimized. Applicability of proposed methods was
verified by analysis of spiked samples of complicated matrices
(river water, urine) and pesticide preparation containing TCP salt.
Further, the influence of potential interfering agents including
selected heavy metals, pesticides and biomolecules possibly
occurring in tested matrices was investigated.
2. Experimental
2.1. Reagents and materials
All used chemicals were of p.a. purity. Triclopyr of 99.9% purity
declared by producer (Sigma–Aldrich, Germany) was used as
received without any further purification. The standard solution of
0.01 mol L1 TCP was prepared by dissolution of an appropriate
amount of TCP powder in 50% acetonitrile (Lach-ner, Neratovice,
Czech Republic). The solution was stored in the dark in a
refrigerator. Working solutions of TCP were prepared fresh daily
by diluting of the standard solution in the supporting electrolyte.
Sulphuric, hydrochloric, and nitric acid and Britton–Robinson
buffer solution (BRBS), consisting of 0.2 mol L1 NaOH and the
same concentration (0.04 mol L1) of orthophosphoric, boric and
acetic acid (all these chemicals Lachema, Brno, Czech Republic),
were tested as supporting electrolytes. All solutions were prepared
in distilled water.
Standard solutions of potential interfering agents, which could
be present in the biological samples, such as ascorbic acid (AA),
barbituric acid (BA), glucose (G), creatinine (C), sucrose (S), and
urea (U) (all Sigma Aldrich, Czech Republic), were prepared in
distilled water. Solutions of folic acid (FA, Sigma Aldrich, Czech
Republic) and uric acid (UA) were, due to the better solubility in the
alkaline media, dissolved in 0.01 mol L1 NaOH. The solutions of
the heavy metal ions (Tl+, Zn2+, Pb2+, Cu2+, and Cd2+) were also
prepared by dissolving of the appropriate amount of their salts (Zn
(NO3)2  2H2O, Pb(NO3)2, CuCl2  2H2O, and Cd(NO3)2  4H2O (all
Lachema, Brno, Czech Republic)) in the distilled water or by
dilution of the calibration standard solution (TlNO3 (Analytika,
Prague, Czech Republic)). The stock solutions of herbicides (all
Sigma Aldrich, Czech Republic; clopyralid (CLP), picloram (PCR),
triasulfuron (TS) and linuron (LIN)) were prepared by dissolving of
the calculated amount of the herbicide in 50% acetonitrile (Lach-
ner, Neratovice Czech Republic); glyphosate (GLY; Sigma Aldrich,
Czech Republic) was dissolved in the distilled water.
(1)
2.2. Instrumentation
All measurements were carried out in three electrodes set up,
where AgjAgCljKCl (sat.) served as a reference and platinum wire as
a counter electrode (both Monokrystaly, Turnov, Czech Republic).
BDD electrode inserted in polyether ether ketone body with inner
diameter of 3 mm, resistivity of 0.075 V cm and B/C ratio during
deposition step of 1000 ppm (declared by Windsor Scientific,
Slough Berkshire, United Kingdom as a producer) was used as a
working electrode in all experiments. The voltammetric measure-
ments were performed by AUTOLAB PGSTAT 12 (Metrohm Autolab,
The Netherlands) potentiostat/galvanostat controlled by NOVA
1.10 software. All measurements were carried out at laboratory
temperature (23  2  C). The pH values were measured by pH-
meter Hanna 221 (Hanna Instruments, USA).
2.3. Procedures
2.3.1. Voltammetric measurements
In the first set of experiments – effect of supporting electrolyte
and scan rate – cyclic voltammetry (CV) scans were measured
between 1.0 V and +2.2 V at scan rate (v) of 100 mV s1 and linear
sweep voltammetry (LSV) measurements were carried out with
initial potential (Ein) 0 V, final potential (Efin) +2.4 V and v = 10
 1000 mV s1. DPV was used with the following working
parameters (if not stated otherwise): Ein = +0.6 V, Efin = + 2.2 V,
step potential of 0.01 V, v = 20 mV s1, modulation amplitude of
0.075 V and modulation time of 0.025 s. SWV was applied with the
subsequent working parameters (if not stated otherwise): Ein =
+1.0 V, Efin = +2.3 V, step potential of 0.05 V, amplitude 0.04 V and
frequency 50 Hz. All DP and SW voltammetric measurements were
carried out in BRBS pH 2.0.
At the beginning of every work day, the surface of BDD electrode
was rinsed with deionized water and anodically pretreated by
applying +2.0 V during 60 s in 1 mol L1 HNO3 solution followed by
2.0 V for 60 s. Finally, 20 cyclic voltammograms from 1.0 V to
+2.0 V in 1 mol L1 HNO3 were measured to obtain stable response.
Between individual measurements, the solution was stirred for 5 s.
The linear least-square regression in OriginPro 9 (OriginLab
Corporation, USA) was used for the evaluation of calibration curve
and the relevant results (slope and intercept) were reported with
confidence interval for 95% probability. The limit of detection
(LOD) and quantification (LOQ), respectively, was calculated as
three times (LOD) and ten times (LOQ), the standard deviation of
 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429
the current for the blank solution (supporting electrolyte) divided
by the slope of the calibration curve. Excel 2010 software
(Microsoft, 2010) was used for construction of the graphical
dependences.
All recorded peaks were evaluated from the straight line
connecting the current minima before and after the peak.
2.3.2. Preparation of the samples
The sample of the tap water came from the water supply in
Pardubice, Czech Republic. Samples of river water were sampled
from rivers Chrudimka and Elbe (Labe) in Pardubice, Czech
Republic. All analyzed water samples were spiked to a concentra-
tion level of 5  106 mol L1. Then, 10 mL of the spiked sample was
transferred into the volumetric flask and filled up with BRBS pH
2.0 to 20 mL. The diluted sample was analyzed. The content of
added TCP was five times determined by standard addition
method.
Human urine sample originated from 29 years old female non-
smoker volunteer. The sample was stored in the refrigerator after
sampling (about 16 hours) and analyzed without any further
pretreatment only after simple dilution. The urine sample was
spiked to the concentration of 400 mmol L1 and 1 mL of the spiked
sample was filled up to 20 mL with BRBS pH 2.0 and analyzed using
standard addition method.
Pesticide preparation Garlon New1 with declared content of
TCP triethylamin salt of 60 g L1 originated from AgroBio Opava,
Czech Republic. 1 mL of the preparation was filled up to 25 mL with
50% acetonitrile and 20 mL of the solution was added to the
polarographic cell with 20 ml of the mixture of BRBS (pH 2.0) and
acetonitrile (3:1, v/v). Addition of acetonitrile was necessary to
ensure sufficient dissolution of other organic species contained in
Garlon New1. The content of TCP in the samples was determined
by standard addition method, when two standard additions were
added at least. Every determination was repeated five times and
relative standard deviation of five repeated determinations (RSDD)
was calculated. The content was calculated as amount of the TCP
triethylamin salt.
3. Results and discussion
3.1. The influence of supporting electrolyte
Generally, a selection of suitable supporting electrolyte is an
essential step in the voltammetric analysis. Supporting electrolyte
A B
30
I/μA
BRBS (pH 2.0)+TCP
BRBS (pH 3.0)+TCP
BRBS (pH4.0)+TCP
BRBS (pH 5.0)+TCP
20 BRBS (pH 6.0)+TCP
BRBS (pH 7.0)+TCP
BRBS (pH 8.0)+TCP
BRBS (pH 9.0)+TCP
BRBS (pH 10.0)+TCP
10 BRBS (pH 11.0)+TCP
BRBS (pH 12.0)+TCP
0.05 M HNO₃+TCP
0.01 M H₂SO₄+TCP
1M HCl+TCP
0 0
-10
-1 -0.5 0 0.5 1 1.5
E vs (Ag|AgCl)/V
Fig. 1. Cyclic voltammograms of TCP in BRBS pH 2.0–12.0, 0.05 mol L1 HNO3, 0.01 mol L1 H2SO4 and 1 mol L1 HCl (A) and CV in the absence and presence of TCP recorded in
BRBS (pH 2.0) (B) using BDD electrode. Inset (B): Dependence of peak height (Ip) on pH of the supporting electrolyte; supporting electrolyte: H2SO4 (1, 0.75, 0.5, 0.1, 0.05,
0.01 mol L1) and BRBS (pH 2.0–12.0), respectively; c(TCP) = 0.244 mmol L1.
423
can modify the thermodynamics and kinetics of electrochemical
processes and charge transfer within the cell and thus significantly
affect ongoing electrode reactions.
The effect of various acids such as nitric, sulphuric and
hydrochloric, respectively, and BRBS of variable pH from 2.0 to
12.0 on voltammetric behavior of 0.244 mmol L1 TCP was
investigated in the whole working potential range on BDD
electrode. Using CV it was found that TCP provides one pH-
independent, very positively situated anodic signal at about +1.9 V
and one indistinctive broad cathodic signal at about 0.2 V in the
reverse scan (Fig. 1). The cathodic signal did not increase
adequately with added TCP. It was also much lower than provided
oxidation signal and thus, it was not further examined for
analytical purposes. Both electrode processes (anodic and cathodic
as well) should be regarded as electrochemically irreversible
because any corresponding signal was not recorded in the reverse
scan. The anodic signal was chosen for further analytical
investigation.
Using HCl as an electrolyte, no signal in the presence of TCP was
recorded due to the earlier onset of the voltammetric curve caused
by oxidation of chloride ions [54] (illustrated with Fig. 1A). One
oxidation signal was detected also in solutions of oxoacids.
Insignificant shift of peak position to more positive potentials
(from +1.88 V (0.01 mol L1 H2SO4) to +1.95 V (1 mol L1 H2SO4); for
HNO3 almost identical shift) and decrease (about 10% (H2SO4) and
12% (HNO3), respectively) of the peak height was observed with
increasing concentration (decreasing pH value) of oxoacids. For
H2SO4 this dependence is shown in the inset of Fig. 1B.
In BRBS the anodic peak is recordable and evaluable in the
whole investigated pH range 2.0–12.0. The positioning of the signal
is constant (+1.89 V), as obvious from CVs at Fig. 1A. The shape and
the height of the signal, respectively, are significantly influenced by
the onset of voltammetric background current. The peak height
decreases rapidly with increasing pH until pH 5.0 and then it does
not change its height significantly (inset of Fig. 1B). Nevertheless,
this decline is caused by the earlier onset of decomposition of
supporting electrolyte solution when increasing its pH, that
influences the baseline used for evaluation (details in chapter
2.3.1). In fact, the absolute value of the peak current is variable only
within  10% for pH 2.0–10.0 suggesting analogous electrode
process independent on the pH. The most favorable shape of the
voltammetric response was recorded in BRBS of pH 2.0 (the
obtained cyclic voltammogram is depicted in Fig. 1B) and thus, this
medium was applied for all next experiments.
15
I/μA
8
Ip/μA
TCP in H₂SO₄
7
TCP in BRBS
10 6
5
4
5
-0.5 2 4.5 7 9.5 12
pH
BRBS (pH 2.0)
BRBS (pH 2.0)+TCP
-5
2 2.5 -1 -0.5 0 0.5 1 1.5 2 2.5
E vs (Ag|AgCl)/V
424 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429
3.2. The effect of scan rate
The influence of scan rate (v) on the voltammetric signal of TCP
was studied using model solution of 0.244 mmol L1 TCP in BRBS
pH 2.0. As expected, the response of TCP increases with increasing
v in the range from 10 to 1000 mV s1 (Fig. 2). Linear dependence
was obtained between the peak height and the square root of the
scan rate (v1/2), which is obvious from the inset of Fig. 2 and Eq. (2)
with coefficient of determination R2 = 0.9981.
Ip/mA = (0.6252  0.0070) (v/mV s1)1/2 – 1.37  0.13
Thus, the anodic process is diffusion controlled, which is
common for BDD electrodes due to a low adsorption of the
electroactive compounds or their product on the working surface
[22,23]. Moreover, the shift of the signal to more positive potentials
with increasing v excludes the reversibility of the electrode
process.
3.3. Mechanism of TCP oxidation
Based on the previously described CV experiments and studies
on electrochemical oxidation of chloromethylphenoxy herbicides
[39], the mechanism of TCP (1) oxidation can be speculated,
depicted at Fig. 3. The pH-independence of the oxidation process
suggests that the anodic peak at ca. +1.9 V corresponds to fast, rate-
determining one-electron oxidation step, forming a cation-radical
(2). At this point it should be noted that this process is not
influenced by the ionization of TCP molecule, taking account on the
pKa values of TCP. These are 2.68 [55] for carboxylic group; the pKa
value for the TCP pyridinium cation was not found in the literature,
nevertheless for structurarly similar chloropyridine derivatives
substituted with carboxylic group these are in the range from 3.2 to
4.4 [18], i.e. lower pKa values than the pKa value of pyridinium
cation itself (pKa = 5.23). It is caused by electron-withdrawing
effect (I effect) of the chloro substituents and I and M effect of
the carboxylic substituent. For TCP with three chloro substituents
and oxyacetic acid substituent (I and +M effect) in the structure
similar value as for above mentioned chloropyridines is expected.
The further reaction step involves quick hydrolysis of the
cation-radical (2) with breaking of the C(1)-O bond to yield
40
I/μA
20
Ip/μA
15
10 q 3.4.1. Optimization of working parameters
30 5 Two pulse voltammetric techniques DPV and SWV, respectively,
0 were chosen for voltammetric analysis of TCP. Model solution of
0 10 20 30 40
(v/mV s-1)1/2
20
10
a step potential was changed from 1 to 10 mV, and the remaining
0
0 0.6 1.2 1.8
E vs (Ag|AgCl)/V
Fig. 2. The effect of scan rate (v) on linear sweep voltammograms of TCP measured
for v (mV s1): a) 10, b) 20, c) 30, d) 40, e) 50, f) 75, g) 100, h) 150, i) 200, j) 300, k)
400, l) 500, m) 600, n) 700, o) 800, p) 900 and q) 1000, respectively; supporting
electrolyte: BRBS (pH 2.0); c(TCP) = 0.244 mmol L1. Inset: Dependence of peak
height (Ip) on the square root of the scan rate (v1/2).
corresponding phenoxy radical (3) and 2-hydroxyethanoic acid as
reaction products. The further fate of the radical can include
stabilization in the phenolic form (4, 2-hydroxy-3,5,6-trichlor-
opyridine) or subsequent reaction of the radical and/or its
oxidation products under formation of polymeric products. This
mechanism is supported by the fact that structurally related
clopyralid (3,6-dichloropyridine-2-carboxylic acid) with carboxyl
group on C(2) instead of the oxyacetic group in TCP and thus
lacking the C(1)—O bond is not oxidizable at BDD electrodes as we
revealed using variety of supporting electrolytes. On the other
(2)
hand for chloromethylphenoxy herbicides with oxycarboxylic
groups at C(2) analogous mechanism was suggested for their
oxidation peak at the potential of +1.55 V–+1.66 V vs. standard
hydrogen electrode at anodically pretreated BDD electrode in
acidic media [39].
The broad cathodic signal at about 0.2 V (Fig. 1) was recorded
only in the reverse cathodic scan, i.e., it was absent when the initial
potential was 0 V and cathodic scan was performed. Thus, it must
be related to products of electrochemical oxidation of TCP.
Presumably, the HO radicals generated in the region of water
decomposition reaction (Eq. (1)) oxidize further the products of
TCP oxidation. A number of studies on photocatalytic degradation
of related chloromethylphenoxy herbicides, chloropyridines
[56,57], and their derivatives including triclopyr [58–60] and
clopyralid [61] revealed that the electrophilic attack of HO on the
pyridine ring may lead to release of the chloride [56,60] and/or to
formation of hydroxypyridines, and further to quinonic and
ketonic structures [39,57], or even to ring opening [39].
Electrochemical incineration of chloromethylphenoxy herbicides
using anodic oxidation at BDD anode by means of HO leads to
formation of corresponding phenol derivatives and their further
hydroxylation with benzoquinones as byproducts of HO iniciated
oxidation [39]. Also in this case, loss of chloride ion may occur.
Similar processes in TCP oxidation would lead to quinoinic
structures, easily electrochemically reducible at and thus possibly
visualized as cathodic signal in the reverse cathodic scan. We
confirmed experimentally that this cathodic signal is negligible
when the vertex potential is close to the signal maxima (i.e., at
+2.0 V), when the amount of electrogenerated HO radicals capable
of further oxidation of reaction products of TCP is minimal
(Fig. SI1 in Supporting Information). Naturally, further studies are
needed to confirm these suggestions on reaction mechanism.
3.4. Analytical performance
50 mmol L1 TCP and BRBS of pH 2.0, respectively, was chosen for
all experiments and the following working parameters were
optimized: DPV – scan rate (v), modulation amplitude and
modulation time; SWV – frequency (f), amplitude (A) and step
potential.
Working parameters of SWV were examined at first. When the
parameters were constant (f = 25 Hz, A = 20 mV), the recorded
signal increased rapidly until the value of 5 mV followed by
slowlier increase from 6 to 10 mV. The step potential of 5 mV was
chosen for next experiments. The influence of amplitude was
2.4 studied in the range from 20 to 140 mV (remaining parameters:
step potential 5 mV, f = 25 Hz). The signal of TCP rapidly increased
until A = 60 mV reaching the height of 4.35 mA and then limited to
the value of about 4.75 mA. Nevertheless, the peak became wider
and deformed at higher values of A (120 and 140 mV) and thus the
amplitude of 40 mV was chosen for all following experiments.
When the frequency changed from 10 to 200 Hz (step potential
 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429 425

Fig. 3. The proposed mechanism of TCP oxidation.

5 mV, A = 20 mV) the peak current increased linearly to the value (SWV), respectively, and relevant voltammetric curves are shown
f = 30 Hz. Further increase of f led to deceleration of the growth in Fig. 4. Obviously, peak heights increase linearly in the given
accompanied by peak widening. Thus, f = 25 Hz was selected for all concentration ranges and thus these can be marked as linear
subsequent experiments. dynamic ranges (LDR) of tested methods. Linearity of calibration
For DPV the scan rate was changed from 10 to 150 mV s1 when dependences is described by Eqs. (3) for DPV and (4) for SWV,
the other parameters remained constant (modulation amplitude respectively, and calculated LODs and LOQs, are given in Table 1.
75 mV, modulation time 25 ms) and significant growth of the peak
Ip/mA = (0.0496  0.0028) c/mmol L1 + 0.033  0.013; R2 = 0.999
was recorded in the range 10  50 mV s1 with deformation of the
(3)
peak from v = 40 mV s1. Therefore, v = 20 mV s1 was chosen as
optimal. Modulation amplitude was investigated from 5 to 200 mV
(other parameters: v = 20 mV s1, modulation time 25 ms) and
Ip/mA = (0.0842  0.0010) c/mmol L1 + 0.031  0.051; R2 = 0.9981
75 mV was selected for further analysis, because the signal was
(4)
easily evaluable, stable, and well-developed. Concerning the
modulation time, decrease of the peak was observed when Nevertheless, the repeatability of TCP determination (c = 5
increasing the parameter in the range 10–100 ms and thus mmol L1) was firstly tested in model solutions by both proposed
25 ms was chosen for all subsequent measurements. techniques using standard addition method. Obtained results and
calculated relative standard deviations of five times repeated
3.4.2. Analytical figures of merit determinations (RSDD) are summarized in Table 2. It is obvious that
The analytical performance of BDD electrode was investigated
using both voltammetric techniques. At first, the repeatability of Table 1
peak height was calculated from 15 repeated scans at TCP Limits of detection and quantitation and linear dynamic range for TCP determina-
tion using DPV and SWV.
concentration 50 mmol L1. Excellent relative standard deviations
of repeated measurements (RSDM), which did not exceed 3% (0.98% DPV SWV
(DPV) and 2.79% (SWV), respectively) were obtained. LOD/mmol L1 0.82 1.85
Calibration dependences for TCP concentrations in the range LOQ/mmol L1 2.72 6.16
from 1.0 to 108.8 mmol L1 (DPV) and from 2.5 to 99.0 mmol L1 LDR/mmol L1 1.0–108.8 2.5–99.0

A B
13
I/μA

8
I/μA

10
Ip/μA

10
Ip/μA

0.6
Ip/μA

8 0.3
8
7 11 p 6
w 6 0.0
0 5 10
4 c/μmol L-1 4
6
2 9 2

0 0
5 0 40 80 120
0 40 80 120 7
c/μmol L-1 c/μmol L-1
4
5
3
a
a
3
2

1 1
1.6 1.8 2 2.2 2.4 1.6 1.8 2 2.2 2.4
E vs (Ag|AgCl)/V E vs (Ag|AgCl)/V

Fig. 4. Effect of various concentration of TCP on its voltammetric response measured using DPV (A) and SWV (B), respectively, on BDD electrode. (A) c(TCP): a) 0, b) 1.0, c) 2.0,
d) 3.0, e) 4.0, f) 5.0, g) 6.0, h) 7.0, i) 8.0, j) 9.0, k) 10.0, l) 15.0, m) 20.0, n) 24.9, o) 29.9, p) 39.8, q) 49.8, r) 59.6, s) 69.5, t) 79.4, u) 89.2, v) 99.0, w) 108.8 mmol L1; Inset:
Dependence of peak height (Ip) on TCP concentration (c). (B) c(TCP): a) 0, b) 2.5, c) 5.0, d) 7.5, e) 10.0, f) 15.0, g) 20.0, h) 24.9, i) 29.9, j) 39.8, k) 59.8, l) 59.6, m) 69.5, n) 79.4, o)
89.2, p) 99.0 mmol L1, Inset: Dependence of peak height (Ip) on TCP concentration (c).
426 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429

Table 2 Table 3
Results of repeated determinations (n = 5) of TCP in model solutions using DPV and Influence of potential interfering agents on the peak height of TCP using DPV at BDD
SWV, at BDD electrode. electrode.

DPV SWV Change of height of TCP peak in the presence of interferent/%

Added/mmol L1 5.00 5.00 TCP: interferent ratio
Found/mmol L1 5.02  0.07 5.04  0.04
Recovery/% 99.0–101.8 100.0–101.6 Interferent 1:1 1:10 1:100
RSDD/% 1.98 1.15 AA +2.7 +3.0 -14.0
BA +2.3 +2.5 +4.8
FA 13.3 a a
obtained results confirmed high recovery, accuracy, and good G +4.0 +3.3 +3.8
repeatability of the determinations. C 0.8 12 b
DPV provided slightly lower detection limit and wider LDR, the S +1.1 1.3 16.6
U +1.5 +4.2 +0.6
followed signal was easily evaluable and thus, it was chosen for
UA 1.8 +3.9 9.6
interference studies and analysis of natural and biological samples Cu2+ 1.1 +2.3 +3.7
spiked with TCP and determination of TCP in the pesticide Cd2+ +0.8 +3.3 3.0
preparation. Pb2+ +4.9 3.4 +1.3
Zn2+ 0.5 8.4
It follows from comparison of LOD in the 107 mol L1 +1.0
Tl+ 6 35.1 59.8
concentration range that similar LODs were achieved at unmodified 1:0.1 1:1 1:5
BDD electrodes for voltammetric or amperometric detection of CLP 0.3 0.9 +1.2
various pesticides including kresoxim-methyl [40], dimetomorph PCR +1.8 25 88
[41], phenolic compounds and nitrophenols [46,47], mancozeb [48], GLY 0.6 +3.3 10.7
TS +10.8 a a
or picloram [50]. More examples are given in reviews [27,62].
LIN +0.2 4.2 a
Moreover, some recent applications of bare BDD electrodes proved
a
higher sensitivity and very low LODs for differential pulse or square Interference of TCP peak with interferent oxidation signal.
b
wave voltammetric determination of various pesticides; e.g. TCP peak not evaluable due to the earlier onset of voltammetric background
current.
4.1 108 mol L1 for carbaryl [37], 1.0  108 mol L1 for atrazine
[42], 8.2  109 mol L1 for parathion [43], and 1.5  109 mol L1
for paraquat [49]. Application of BDD electrode, as an electrochem- and substituted aromatic compounds [63] including e.g. pyridine
ical detector for carbamate pesticides after high performance liquid dicarboxylates [64], presumably it interacts with TCP in the solution
chromatographic separation, provided very low (nanomolar level) and thus influences its electrochemical behavior. Zn2+ also partly
LODs as well [38]. influences the TCP response but only at higher excess.
Among tested herbicides, CLP did not interfere despite similar
3.4.3. Interference study structure due to the absence of oxidation signal, as highlighted in
The selectivity of proposed DPV procedure was investigated the chapter 3.3. PCR interferes seriously especially at the same and
under optimal working conditions at the same concentration of five times higher concentration due to its oxidizability at high
TCP (10 mmol L1). Selected biomolecules, which could be present anodic potential at BDD as we proved recently [50–53]. Also
in the biological samples, heavy metals and few often used substituted ureas interfere during voltammetric analysis of TCP on
herbicides, which could occur in the natural samples or in pesticide BDD electrode. LIN provides one oxidation signal, which is situated
preparations, were used as possible interfering agents. Heavy more positively but it seriously influences TCP response at fivefold
metals as Cu2+, Cd2+, Pb2+, Zn2+, and Tl+ and biomolecules as excess. TS gives one anodic peak at almost identical potential,
ascorbic acid (AA), barbituric acid (BA), folic acid (FA), glucose (G), which makes impossible the correct evaluation of the TCP signal.
creatinine (C), sucrose (S), urea (U), and uric acid (UA) were added Obtained voltammograms for the concentration ratio 1:1 are
in the concentration ratios (TCP:interferent) 1:1, 1:10 and 1:100, depicted in Fig. SI4 in Supporting Information.
respectively. Various herbicides as structurally related clopyralid
(CLP) and picloram (PCR), wide-spread used herbicide glyphosate 3.4.4. Determination of TCP in real and spiked samples
(GLY), and substituted ureas triasulfuron (TS) and linuron (LIN), Applicability of the proposed DP voltammetric method was
were analyzed at ten times lower, the same and five times higher verified by analysis of spiked samples as tap water and river waters
concentration level than TCP. The compound was considered to (Elbe and Chrudimka) and urine, because it is the principal excretion
interfere seriously, if the height of TCP anodic peak changed 5% or route for nonmetabolized TCP [65–67]. Carmichael et al. [65]
more. These critical values are highlighted in bold script in Table 3 investigated oral and dermal pharmacokinetics of TCP in human
summarizing obtained results. volunteers. The authors ascertained that more than 80% of the dose
Concerning biomolecules, TCP response is mostly influenced in was found as unchanged TCP in the urine. The analysis of blank
the presence of FA when 10 or 100fold excess of FA is present; the samples proved that any of the studied matrices did not contain
TCP response is not possible to evaluate correctly because FA measurable amount of TCP or related compounds, which could
provides an interfering signal as illustrated in Fig. SI2 in Supporting disturb the determination and therefore, all samples were spiked
Information. This figure shows voltammograms of 10 mmol L1 TCP with TCP as it is described above in the chapter 2.3.2. Obtained results
in presence of the tested biomolecules in the concentration ratio of are summarized in Table 4 and the representative voltammograms
1:10. AA and UA also provide one oxidation peak, but they for determination of TCP in human urine using standard addition
influence the TCP response only at the highest, 100fold excess. The method are depicted in Fig. 5A. The high recoveries confirm that the
same excess of C and S, causes earlier onset of voltammetric proposed method is applicable for analysis and correct and accurate
background current, which makes worse (S) or even impossible (C) determination of TCP even in very complicated matrices like natural
the evaluation of the TCP signal. waters or human urine. On the other hand, we can also conclude that
From tested heavy metals, only Tl+ influences seriously the TCP complicated matrix, especially urine, worsens possibilities to detect
response due to enhancement of anodic signal at very positive low concentrations of TCP and thus a preconcentration step e.g. using
potentials, as obvious from Fig. SI3 in Supporting Information. solid phase extractionwould be necessary for determination of lower
Because Tl+ has predisposition to form complexes with heterocyclic concentrations.
 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429 427

Table 4
Results of repeated determinations (n = 5) of TCP in the spiked water and urine samples and in the pesticide preparation Garlon New1 using standard addition method and
DPV at BDD electrode.

Sample Added/mmol L1 Found/mmol L1 Recovery/% RSDD/%

Tap water 5.00 4.98  10 97.6–101.6 3.12
River 5.00 5.01  0.09 98.4–102.0 2.84
Elbe
River 5.00 4.97  0.09 97.6–101.2 2.63
Chrud.
Human urine 400.0 418.8  19.9 99.7–109.7 7.17

Declared/g L1 Found/g L1 Recovery/% RSDD/%

1
Garlon New 60.00 58.97  5.21 89.6–107.0 8.97

A B
8 2
I/μA

I/μA
urine+TCP
Garlon New ®
1st standard addion
1st standard addion
2nd standard addion
2nd standard addion
3rd standard addion
4 1

1 0
0.6 1 1.4 1.8 2.2 1.1 1.5 1.9 2.3

E vs (Ag|AgCl)/V E vs (Ag|AgCl)/V

Fig. 5. Voltammetric analysis of spiked human urine (A) and pesticide preparation Garlon New1 containing TCP triethylamin salt (B) using DPV at BDD electrode. The
voltammograms of analysis of Garlon New1 are shown after baseline correction.

The sample of pesticide preparation Garlon New1 was prepared
as it is described in the chapter 2.3.2. Due to the decrease of the TCP
signal during repeated analysis, which was caused probably by
contamination of the electrode surface by the organic species
contained in the matrix (besides TCP salt also 20 g L1 fluoroxypyr
and some additives such as solvent naphtha, petroleum (unspeci-
fied), ethoxylated alcohols C12–C15 and 1,2,4-trimethylbenzen),
the mixture of 15 mL BRBS (pH 2.0) and 5 mL acetonitrile was used
as the supporting electrolyte. Addition of acetonitrile was
necessary to ensure sufficient dissolution of these organic species
and prevent electrode fouling. Fig. 5B illustrates obtained
voltammetric curves after baseline correction, which was applied
for easier evaluation. From results in the Table 4, it is evident that
determined amount corresponds with declared amount of TCP salt,
which confirms suitability of tested method for analysis of the
pesticide preparation.
4. Conclusion
Electrochemical behavior of TCP, a pyridine herbicide, has been
investigated for the first time. Bare BDD electrode enabled due to
its wide potential window in anodic region a diffusion-controlled
irreversible oxidation of TCP at the potential of ca. +1.9 V. The
electrode reaction initiated presumably by pH-independent one
electron charge transfer to yield corresponding phenoxy radical is
utilizable for analytical purposes. The limits of detection of the
proposed differential pulse and square wave voltammetric
methods are in the micromolar concentration range. Whereas,
any voltammetric method has not been proposed yet for
determination of TCP, we can only compare published results
for structurally similar chloro-substituted pyridine carboxylic
acids, including picloram. These are reducible at mercury-based
electrodes with ca. comparable [19] or about eight times lower
LODs [20] then achieved for TCP in this study. For PCR, similar LOD
of 0.07 mmol L1 [50] and 1.64 mmol L1 [53], respectively, was
reported in our previous studies using BDD electrodes. The
selectivity of proposed method was investigated in the presence
of various substances, which could occur in the environmental or
biological samples. It was found that especially folic acid, thallium,
picloram and substituted ureas interfere seriously and thus, the
applicability of the proposed DP voltammetric procedure with
optimized parameters was verified by analysis of spiked human
urine and environmental samples, respectively, and by analysis of
pesticide preparation containing TCP salt. The obtained high
recoveries confirm that voltammetry at unmodified BDD electrode
represents reliable, sensitive and environmental friendly analytical
technique for determination of TCP.
Acknowledgement
This work was supported by The Ministry of Education, Youth
and Sports of the Czech Republic (project No. CZ.1.07/2.3.00/
30.0021 “Enhancement of R&D Pools of Excellence at the
University of Pardubice”) and by Grant Agency of the Czech
Republic (project GACR P206/12/G151).
428 L. Janíková-Bandžuchová et al. / Electrochimica Acta xxx (2015) 421–429
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