Short Communication
DOI: 10.1002/elan.201400454
On-Site Determination of Carbendazim, Cathecol and
Hydroquinone in Tap Water Using a Homemade Batch
Injection Analysis Cell for Screen Printed Electrodes
Ricardo Pini Caramit,[a] Bruno Gabriel Lucca,[a] Valdir Souza Ferreira,[a]
Rodrigo Alejandro Abarza Munoz,[b] Eduardo Mathias Richter,[b] and Rodrigo Amorim Bezerra da Silva*[c]
Abstract: In this work, we present a simple homemade
batch-injection analysis cell for screen-printed electrodes
(BIA-SPE). The potential of the proposed system for on-
site analysis was demonstrated by the determination of
carbendazim, catechol, and hydroquinone in tap water.
The system provided reduced injection volume (30 mL),
high analytical frequency (  200 h 1) and low detection
Keywords: Batch injection analysis (BIA) · Screen-printed electrodes · Homemade portable system · On-site analysis
Chemical analysis performed at the place of the sampling
(“in loco” analysis) rather than in a conventional labora-
tory is often attractive. A portable assay method for field
work enables sample collection and data analysis in real-
time, the reduction in time consumption and total analy-
ses costs [1]. Furthermore, portable assays is one of the
main trends in analytical chemistry due to the rapid
growth of the potentials of such analysis [2] and the in-
creasing demands in field analysis for fuel [3], forensic
[4], and environmental [5] samples. In electrochemical
detection, many companies commercialize a series of
portable instruments suitable to in field analysis, as hand-
held potentiostats and screen-printed electrodes (SPEs)
containing a series of modifiers (e.g., multi- and single-
walled carbon nanotubes, graphene, bismuth and Prussian
blue) [6]. These simple devices allows the simple adjust-
ment of SPEs in many electrochemical cells, as batch [7]
and flow [8, 9] systems, as well measurements in drops of
solution (  50 mL) [10]. Other suitable approach to devel-
opment of portable analytical methods is Batch Injection
Analysis (BIA) [11]. This system is based on the injection
of a sample plug through a micropipette tip directly onto
the working electrode surface (wall-jet configuration)
which is immersed in a large-volume of blank solution.
BIA and flow injection analysis (FIA) [12] have high ana-
lytical frequency, low consumption of reagents and sam-
ples. Nevertheless, BIA is more simple and portable, be-
cause the absence of pump, valves and tubes [13]. This
work proposes the use of a very simple and portable
homemade batch-injection analysis cell to accommodate
screen-printed electrodes (BIA-SPE) to determination of
herbicide carbendazim (CZIM), hydroquinone (HQ), and
catechol (CAT) in tap water. The BIA-SPE system has
www.electroanalysis.wiley-vch.de  2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
limits (nanomolar level). Moreover, the BIA-SPE cell
presented better stability (RSD  0.4 %) than a conven-
tional flow injection cell for SPE (RSD  5.0 %) in organ-
ic media. The proposed homemade BIA-SPE cell is very
simple, inexpensive and can be easily constructed in any
laboratory.
capability to increase the applicability of electrochemical
methods for in field analysis.
The BIA-SPE homemade electrochemical cell was con-
structed from an acrylic rod (1i = 4.0 cm, height =
4.0 cm). As presented in Figure 1, a hole (diameter =
3.1 cm; height = 4.0 cm) was drilled from one side of the
rod (top side) and the other side was maintained closed
(bottom side). The top side was closed with an acrylic
cover with two holes. The first was used for insertion/ex-
change of the supporting electrolyte and the second was
used for the reproducible positioning of the 1 mL combi-
tip of electronic pipette (Figure 1). The combitip with
a regular external diameter (6 mm) was firmly introduced
into the hole (diameter = 6.1 mm) in such a manner that
the distance between the pipette tip and the electrode
surface was always the same (highly reproducible injec-
tion procedure). Optionally an insulin syringe also can be
[a] R. P. Caramit, B. G. Lucca, V. Souza Ferreira
Instituto de Qumica, Universidade Federal de Mato Grosso
do Sul
Av. Senador Filinto Mller, 1555, CEP 79.074-460, Campo
Grande, MS, Brazil
[b] R. A. Abarza Munoz, E. M. Richter
Instituto de Qumica, Universidade Federal de Uberlndia
Av. Jo¼o Naves de vila, 2121, CEP 38.408-100, Uberlndia,
MG, Brazil
[c] R. A. B. da Silva
Faculdade de CiÞncias Exatas e Tecnologia, Universidade
Federal da Grande Dourados
rodovia Dourados – Itahum, Km 12 (Cidade Universitria),
Dourados, MS, Brazil CEP 79.804-970
tel: 55-67-3410-2091.
*e-mail: rodrigoamorim@ufgd.edu.br
Electroanalysis 2015, 27, 271 – 275 271
Short Communication

Fig. 1. (A) Schematic diagram and (B) photograph of the homemade BIA-SPE electrochemical cell.

used in a thirty hole to injections of solutions. The SPE
was inserted into the cell through an orifice (width =
0.1 cm; height = 1.08 cm) performed on the cell wall. In
order to prevent leaks, a thermo-polymer (hot-melt adhe-
sive; Tilibra, Brazil) was placed outside the cell. If neces-
sary replacing the SPE, the polymer must be mechanical-
ly removed and then a new SPE must be repositioned
and glued.
The total internal volume of the cell is around 15 mL.
The SPE (DropSens) was composed by a planar carboxyl
functionalized multi-walled carbon nanotubes as working
electrode (1 = 4 mm; geometric area = 0.1257 cm2), and
printed carbon and silver as the counter and pseudo-ref-
erence electrodes, respectively. To compare the perfor-
mance of the proposed cell, amperometric measurements
were also performed with a homemade flow injection cell
for screen-printed electrodes (FIA-SPE) [9].
Firstly, experiments were carried out to find the most
adequate potential for amperometric detection of each
analyte (HQ, CAT or CZIM) in the BIA cell. In these
studies, aliquots of 50 mmol L 1 of analyte solution were
injected holding the electrode at fixed applied potentials
(from 0.3 V to 0.5 V to HQ/CAT and 0.0 to 0.9 to
CZIM). Hydrodynamic voltammograms (Figure 2) were
obtained by plotting the average peak current values (n =
3) as a function of the corresponding applied potential.

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Short Communication

Fig. 2. Plot of the average peak currents obtained after sequen-

tial injections (n = 3) of a solution containing 50 mmol L 1 of each
analyte (HQ, CAT or CZIM) into the BIA-SPE cell as a function
of the applied potential. Supporting electrolyte: HQ and CAT:
0.04 mol L 1 BRB (pH 4); 5 % (v/v) ethanol water with
0.04 mol L 1 BRB (pH 4); dispensing rate: 113 mL s 1; injected
volume: 50 mL; working electrode: MWCNT-SPE (Geometric
area: 0.1257 cm2).

As presented in Figure 2, the oxidation current of

CZIM starts to increase at around 0.5 V and reaches a pla-
teau value at potentials above 0.7 V. At potential more
positive than 0.8 V, higher background currents were ob-
served. Therefore, the potential of 0.8 V was chosen as
the best for the determination of CZIM. In addition, the
hydrodynamic voltammograms for HQ and CAT were
also presented in Figure 2. As can be observed, a maxi-
mum current for HQ and CAT oxidation were obtained
at 0.2 V and 0.4 V, respectively. After, BIA parameters as
dispensing rate (155 mL s 1) and injection volume (30 mL)
were evaluated in order to obtain the highest analytical
signal, best precision, and analytical frequency. These pa-
rameters were defined taking into account the theoretical
justification for wall-jet amperometric configuration pre-
viously reported [14].
In order to evaluate the precision of the homemade
BIA-SPE cell under the optimized conditions, a repeata-
bility study was conducted through successive (n = 20) in-
jections of 50 mmol L 1 CZIM solution.
As presented at Figure 3 A, good repeatability (RSD =
0.4 %; n = 20) was obtained when the electronic micro-
pipette was used in the injection procedure. However,
when in these experiments the electronic micropipette
was replaced by a disposable insulin syringe (Figure 3 B),
the repeatability was much worse (RSD = 4.7 %; n = 20),
because of imprecision of manual injections. In this case,
the use of an internal standard with multiple pulse am-
perometric detection could minimize the fluctuations re-
lated to manual injection variations, as demonstrated in
a previous work [15]. To compare the performance of the
proposed electrochemical cell, twenty successive injec-
tions of CZIM solutions were also performed in a FIA-
SPE system with amperometric detection (Figure 3 C). As
presented, the noise and stability of baseline of FIA-SPE
Fig. 3. Amperometric responses after twenty successive injec-
tions of 50 mmol L 1 CZIM solution in BIA-SPE with electronic
micropipette (A) and insulin syringe (B) and FIA-SPE system
(C). Conditions: (A): dispensing rate: 155 mL s 1; injected
volume: 30 mL (other as in Fig. 2). (C): Injected volume: 50 mL;
Flow rate: 40 mL s 1. Electrolyte: 5 % (v/v) ethanol water with
0.04 mol L 1 BRB (pH 4).
system were worse than BIA-SPE. Moreover, it was
noted a progressive reduction in peak currents (RSD
 5.0 %), and from 21st injection, the working electrode
showed no responses. This unstable behavior occurs prob-
ably due to the continuous flow of the aqueous-organic
electrolyte on MWCNT surface (wall jet configuration).
In this way, the batch configuration of BIA electrochemi-
cal cell proposed is less destructive to screen-printed elec-
trode.
Under optimized conditions of BIA-SPE (injected
volume = 30 mL and dispensing rate = 155 mL s 1), three
calibration curves were obtained for HQ, CAT and
CZIM, respectively. The analytical figures of merit of
each curve were summarized in Table 1. The recovery
values calculated to each analyte in tap water are also
presented in Table 1. As presented, satisfactory sensitivity

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Short Communication
Table 1. Variables, analytical figures of merit and recovery obtained for HQ, CAT and CZIM. LOD: limit of detection; RSD: relative
standard deviation.
HQ
Detection potential (V) [a] 0.30
Linear range (mmol L 1) [b] 0.1–200
Slope (mA mmol 1 L) [b] 0.129
LOD (mmol L 1) [b] 0.02
Correlation coefficient [b] 0.999
RSD (%) [c] 0.87
Analytical frequency (h 1) [c] 190
Recovery (%) [d] 97  2
[a] Selected in accordance with Figure 2. [b] Calculated from respective calibration plots. [c] Calculated from repeatability study (as in
Figure 3 A). [d] Found value by calibration curve/spiked value  100 %.
and low LOD values were obtained, as well good repeat-
ability (RSD < 1 %) and analytical frequency (  200 h 1).
Moreover, appropriated recovery values (between 95 and
105 %) were obtained for the three target analytes stud-
ied.
Previous works reported an improvement in analytical
frequency when solution inside the BIA cell was under
stirring [11, 16], because the enhance of analyte washout
from the electrode surface [11]. However, in this work we
choose not employ magnetic stirrer due to easier trans-
port and use of homemade BIA cell in the field analysis.
Another feature of the BIA-SPE cell is the low size and
internal volume of the cell (15 mL), which presents ad-
vantages as reduction of waste and electrolyte consump-
tion. Moreover, as observed in BIA-amperometric experi-
ments at different cell volumes (not shown) and reports
in literature [17], no changes in current peaks and in
washout properties are observed for cells with different
working volumes.
Recently, some analytical methods based on SPEs
(bare working electrodes or biosensors) associated with
FIA systems have been proposed due to enhanced mass
transport (hydrodynamic flow), speed and reproducibility,
as well advantages in portable characteristics [18]. How-
ever, despite the portable SPEs, it is important to point
out that the FIA components (pump, valves and tubes)
are not so easy to carry to out of laboratory. In this way,
BIA apparatus (electronic microppipete and electrochem-
ical cell) are easier in transport and hand manipulation.
Thus, the homemade BIA cell for SPEs proposed herein
is advantageous in the development of fast and portable
analytical methods. The BIA-SPE cell proposed here is
simpler and easier to build than the cell previously re-
ported by our group [19]. The simplicity of construction
can be useful for other research groups since the cell can
be constructed in a simple mechanical workshop (without
the help of an expert in the field). However, some disad-
vantages compared with the previous cell can also be
cited: (i) greater difficulty in electrode exchange opera-
tion (because of the use of thermo-polymer); (ii) greater
difficulty in positioning a micro DC-motor on the top
cover for solution stirring [15] (due to the lower dimen-
sions of this cell); however, stirring can be supplied by
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CAT CZIM
0.50 0.80
0.1–200 0.2–100
0.136 0.093
0.05 0.06
0.999 0.996
0.38 0.34
270 200
101  2 101  1
a magnetic stirrer bar in this cell; (iii) necessity of a flask
clamp assembly to maintain the BIA cell in standing posi-
tion.
Experimental
Solutions were prepared with deionized water (Direct-
Q3, Millipore, Bedford, MA, USA) with a resistivity no
less than 18.2 MW cm. Hydroquinone (HQ), cathecol
(CAT) and carbendazim (CZIM) were purchased from
Sigma-Aldrich (USA), ethanol from Dinamica (Brazil),
acetic acid, boric acid, phosphoric acid and sodium hy-
droxide from Acros Organics (USA). All reagents used
in this work were of analytical grade. Britton Robinson
buffer (0.04 mol L 1 BRB; pH = 4.0) was used as support-
ing electrolyte for HQ and CAT determination. This solu-
tion was prepared by mixing acetic acid, boric acid and
orthophosphoric acid (0.04 mol L 1 of each) and the pH
was adjusted by additions of a 0.5 mol L 1 sodium hydrox-
ide. For the determination of CZIM, ethanol was added
to 0.04 mol L 1 BRB until reach a 5.0 % (v/v). The stock
solutions of HQ and CAT were prepared in water and
CZIM in ethanol. All solutions were freshly prepared just
before experiments. Tap water was collected from our re-
search laboratory. Each sample was spiked with 200, 250
or 500 mmol L 1 of stock solution of respective analyte
(HQ, CAT or CZIM). Before the injections in the home-
made BIA-SPE cell, the spiked tap waters samples were
diluted 10 times in the same supporting electrolyte used
inside the BIA cell.
Electrochemical measurements were performed using
a PalmSens handheld potentiostat/galvanostat (PalmSens,
Utrecht, The Netherlands) interfaced to a microcomputer
and controlled by PSTRACE 2.2 software. Injections of
solutions were performed with a motorized electronic mi-
cropipette (Eppendorf Multipette stream), which enables
injections from 10 to 1000 mL (with the 1 mL combitip) at
a programmable dispensing rate (from 28 to 350 mL s 1).
The multiwalled carbon nanotube modified screen-print-
ed electrode (MWCNT-SPE) was purchased from Drop-
Sens (Oviedo, Spain) [20]. The MWCNT-SPE was com-
posed by a planar carboxyl functionalized multi-walled
carbon nanotubes as working electrode (1 = 4 mm; geo-
Electroanalysis 2015, 27, 271 – 275 274
Short Communication
metric area = 0.1257 cm2), and printed carbon and silver
as the counter and pseudo-reference electrodes, respec-
tively. Amperometric detection at a constant potential [7]
was used for HQ, CAT and CZIM determination. All
electrochemical measurements were performed at room [8]
temperature, in the presence of dissolved oxygen.
[9]
Acknowledgements [10]
The authors are grateful to Brazilian funding agencies
CNPq (Process Number 475276/2013-2), CAPES, FUN-
[11]
DECT and FAPEMIG for financial support. [12]
[13]
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Received: August 21, 2014
Accepted: October 8, 2014
Published online: December 8, 2014
Electroanalysis 2015, 27, 271 – 275 275