Article

pubs.acs.org/JAFC

Electrochemical Determination of Chlorpyrifos on a Nano-TiO2/

Cellulose Acetate Composite Modified Glassy Carbon Electrode
Ammasai Kumaravel§ and Maruthai Chandrasekaran*,†
†
CSIR−Central Electrochemical Research Institute (CECRI), Karaikudi 630006, Tamil Nadu, India
§
PSG Institute of Technology and Applied Research, Coimbatore 641062, Tamil Nadu, India

ABSTRACT: A rapid and simple method of determination of chlorpyrifos is important in environmental monitoring and quality
control. Electrochemical methods for the determination of pesticides are fast, sensitive, reproducible, and cost-effective. The key
factor in electrochemical methods is the choice of suitable electrode materials. The electrode materials should have good stability,
reproducibility, more sensitivity, and easy method of preparation. Mercury-based electrodes have been widely used for the
determination of chlorpyrifos. From an environmental point of view mercury cannot be used. In this study a biocompatible nano-
TiO2/cellulose acetate modified glassy carbon electrode was prepared by a simple method and used for the electrochemical
sensing of chlorpyrifos in aqueous methanolic solution. Electroanalytical techniques such as cyclic voltammetry, differential pulse
voltammetry, and amperometry were used in this work. This electrode showed very good stability, reproducibility, and sensitivity.
A well-defined peak was obtained for the reduction of chlorpyrifos in cyclic voltammetry and differential pulse voltammetry. A
smooth noise-free current response was obtained in amperometric analysis. The peak current obtained was proportional to the
concentration of chlorpyrifos and was used to determine the unknown concentration of chlorpyrifos in the samples. Analytical
parameters such as LOD, LOQ, and linear range were estimated. Analysis of real samples was also carried out. The results were
validated through HPLC. This composite electrode can be used as an alternative to mercury electrodes reported in the literature.
KEYWORDS: chlorpyrifos, biocompatible modified electrode, electroanalytical sensor, detection limits, real sample analysis

■ INTRODUCTION
Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridinyl)-
within quick adsorption times, compact nature, and easy
handling and deployment in field trials. Even though
phosphorothioate] is an organophosphate insecticide. It electroanalytical techniques are more suitable for monitoring
possesses low water solubility (1.39 mg/L) and a high soil the toxic level of pesticides, unfortunately, less attention is paid
sorption coefficient. Chlorpyrifos, like other organophosphate to the development of electroanalytical sensors for pesticides
compounds, is known to produce toxic effects by inhibiting the such as chlorpyrifos. Very few works on the electrochemical
acetylcholinesterase enzyme activity, which is responsible for determination of chlorpyrifos have been reported. Indirect
the hydrolysis of acetylcholine, which is the key molecule in the determination of chlorpyrifos using a hanging mercury drop
control of cholinergic transmission in the central and peripheral electrode (HMDE) by cathodic adsorptive stripping voltam-
nervous system. It is used to control mosquitoes, flies, various metry,11 differential pulse polarographic analysis,12 and
insects, and pests in domestic and agricultural fields. It is also adsorptive catalytic stripping voltammetric determination
used on sheep and cattle to control ectoparasites.1 The using HMDE13 was reported. It is not advisable to use mercury
agricultural, residential, and commercial use of chlorpyrifos electrodes due to their toxicity. Differential pulse adsorptive
could lead to the accumulation of high concentrations in the stripping voltammetric determination of chlorpyrifos at a
environment.2 Chlorpyrifos persists in soil for 60−120 days and sepiolite modified carbon paste electrode was reported.14
produces toxic effects to human beings and animals.3 Electrochemical studies and square wave stripping voltammetry
Chlorpyrifos is a moderately toxic pesticide when compared of chlorpyrifos on a poly(3,4-ethylenedioxythiophene)-modi-
to many other pesticides.4However, long-term health effects fied wall-jet electrode were reported. The hydrodynamics of the
associated with human exposure to chlorpyrifos are the subject wall-jet electrode is complex.15 Poly(3-hexylthiophene)/TiO2-
of increasing concern in recent years.5,6 based photoelectrochemical sensing of chlorpyrifos16 and a
Many analytical methods such as gas chromatography,7,8 surface molecular self-assembly strategy for molecular imprint-
negative ion chemical ionization gas chromatography, mass ing in electropolymerized polyaminothiophenol membranes at
spectrometry,9 and high-performance liquid chromatography the surface of a gold nanoparticle-modified glassy carbon
were developed for the determination of organophosphorus electrode for the electrochemical detection of pesticide
pesticides.10 However, these analytical methods are time- chlorpyrifos were reported.17 Anodic oxidation of chlorpyrifos
consuming and costly, and also the availability of these high- using lead dioxide was also reported.18
cost instruments in laboratories is limited. Therefore, there is a
need to develop a sensitive, economically viable, portable Received: April 30, 2015
instrument for the analysis of this pesticide. Electroanalytical Revised: June 9, 2015
techniques are more suitable because of their various Accepted: June 15, 2015
advantages such as low cost, selective and sensitive responses Published: June 15, 2015

© 2015 American Chemical Society 6150 DOI: 10.1021/acs.jafc.5b02057

J. Agric. Food Chem. 2015, 63, 6150−6156
Journal of Agricultural and Food Chemistry Article

The solubility of chlorpyrifos in water is very low, and the Preparation of n-TiO2 /CA/GCE. The GC electrode was hand
analysis has to be carried out in toxic solvents such as DMF. polished with fine emery papers (1/0, 2/0, 3/0, 4/0), rinsed
The reduction potential of chlorpyrifos on mercury-based thoroughly with Millipore water, cleaned successively in 10% NaOH
solution, 1:1 HNO3/water (v/v), and MeOH, each for 2 min, and
electrodes is almost close to the hydrogen evolution potential,
dried in air.25 Before modification of the GC electrode, the
which complicates the estimation of sensing currents (peak reproducibility of the bare GC electrode was checked with the
currents). In this work we tried to overcome these recording of cyclic voltammetric responses of a potassium
disadvantages by developing a newer modified electrode for ferrocyanide/ferricyanide redox system in 0.1 M KCl as reported in
the sensing of chlorpyrifos. the literature.26
Due to the high affinity of nano-TiO2 on phosphate groups, Cellulose acetate solution was prepared by following the procedure
it was used as a sensor probe along with nafion for the available in the literature.27,28 Cellulose acetate (0.2 g) was dissolved in
electrochemical sensing of the organophosphate pesticide solvents containing 12.7 mL of acetone and 10.6 mL of cyclohexanone
and stirred for 3 h to get a homogeneous solution.
fenitrothion.19 Cellulose acetate (CA) is a porous material
The modifier solution n-TiO2/CA was prepared by mixing 4 mg of
that is used to immobilize the enzymes, bacteria, and metal nano-TiO2 powder into 4 mL of the above prepared cellulose acetate
nanoparticles. The advantages of CA membrane are good solution and stirred for 1 h. This solution was used for modification of
stability in alcohol-based electrolyte, biocompatibility, easy film- the GC electrode. The GC electrode was coated with 8 μL of n-TiO2/
forming properties, and low cost.20,21 Titanium dioxide CA solution by the drop−dry method. This 8 μL modifier solution
immobilized on a cellulose acetate membrane, a hybrid contains 4.36 μL of acetone, 3.64 μL of cyclohexanone, 8 ng of TiO2
material, shows a very attractive electrocatalytic property and powder, and 0.05264 ng of cellulose acetate. The coated GC electrode
stability in sensor applications.22,23 Nano-TiO2/cellulose was dried in air for 3 h. A very thin film was seen on the GC surface.
acetate is a complex material with no chemical interaction This modified n-TiO2/CA/GCE was used for electrochemical
measurements.

■
between TiO2 particles and cellulose acetate, which are only
physically mixed. However, very few studies were available in RESULTS AND DISCUSSION
the literature using this composite modified electrode in sensor
applications. Studies on the analysis of pesticides on this Surface Morphology of n-TiO2/CA/GCE. An SEM image
composite modified electrode were not reported in the of the composite modified GCE is shown in Figure 1. From the
literature.
In this paper, we report the preparation, characterization, and
application of a nano-TiO2/cellulose acetate modified glassy
carbon electrode (n-TiO2/CA/GCE) for the electrochemical
sensing of chlorpyrifos. SEM was used for surface character-
ization. Cyclic voltammetry, differential pulse voltammetry, and
amperometry were used as sensing techniques.

■ EXPERIMENTAL PROCEDURES
Apparatus. Cyclic votammetry (CV), differential pulse votamme-
try (DPV), and amperometry were performed with the computer-
controlled Autolab PGSTAT 30 (Eco Chemie, Utrecht, The
Netherlands) electrochemical system. DPV was recorded with the
following optimized instrumental settings: modulation amplitude, 40
mV; modulation step, 4 mV; and set scan rate, 8 mV s−1. For
electrochemical experiments, a 10 mL glass cell with a TiO2/cellulose
acetate coated glassy carbon electrode (GCE Alfa Aesar, 3 mm
diameter) as the working electrode, platinum foil as the counter
electrode, and saturated calomel electrode (SCE) as the reference
electrode was used. SEM analysis was done with a Hitachi model S- Figure 1. SEM image of n-TiO2/CA/GCE.
3000H with 20 kV acceleration voltage. HPLC analysis was carried out
with an LC-10AT pump and an SPD-10A detector (Shimadzu, Kyoto, figure, it can be seen that the composite film uniformly covered
Japan) at 254 nm with a Shimpack CLC ODS-18 column. Prior to
electrochemical measurements, the solution was deareated by purging
the surface of the GCE with pores and shrinking of the film.
with pure nitrogen for 15 min. All electrochemical experiments were The nano-titania particles are spread on the surface.
carried out at 30 ± 1 °C. Optimization of Modified Electrode Preparation. The
Reagents and Chemicals. Chlorpyrifos was purchased from volume of nano-TiO2/cellulose acetate solution used for
AccuStandard, New Haven, CT, USA. A stock solution of chlorpyrifos modification of the GCE surface was optimized by recording
(2424 μM) was prepared in methanol. Tetra-n-butyl ammonium cyclic voltammetry of 50 μM chlorpyrifos in 0.05 M on n-
bromide was purchased from Alfa Aesar, and its 0.05 M solution was TiO2/CA/GCE in TBAB 60:40 methanol/water (Figure 2).
prepared in 60:40 methanol/water (v/v). It was used as the solvent− The peak current increases with the increase in the volume of
supporting electrolyte system. The nano-TiO2 powder was prepared as nano-TiO2/cellulose acetate solution up to 8 μL. A further
follows, and the details are available in the literature.24 Titanium(IV) increase in the volume of nano-TiO2/cellulose composite
butoxide (10 g) was dissolved in cyclohexanol solvent. To this solution
a premixed solution containing water, cyclohexanol, and hexadecyl-
solution on GCE results in a decrease in the peak current value.
trimethylammonium bromide was added at room temperature. After This may be due to the formation of thicker films, which may
12 h, triethylamine was added to precipitate TiO2 powder. The TiO2 render the mass transport difficult, so the optimum volume of 8
powder was separated, washed with acetone, and dried in air at 353 K μL was used to modify the electrode surface.
for 2 h. The dried powder was calcined at 773 K to give nano-TiO2 Cyclic Voltammetric Analysis. Figure 3 shows the cyclic
powder. Other reagents used were of analytical reagent grade. voltammetric response of 50 μM chlorpyrifos at n-TiO2/CA/
6151 DOI: 10.1021/acs.jafc.5b02057
J. Agric. Food Chem. 2015, 63, 6150−6156
Journal of Agricultural and Food Chemistry Article

root of the scan rates reveals that the reduction process is

diffusion controlled. The reduction of CN of the pyridine
ring is difficult and occurs very close to the hydrogen evolution
region and sometimes completely overlaps with the background
reduction, that is, hydrogen evolution. However, the attach-
ment of three chlorine atoms in the pyridine ring delocalizes
the electrons at the −CN− bond and, consequently,
enhances the reduction of the −CN− bond of the pyridine
ring at lesser negative potentials.11 However, studies on the
direct reduction of chlorpyrifos are limited. The reduction of
chlorpyrifos was carried out on the bare glassy carbon electrode
(Figure 3a), cellulose acetate modified GCE (Figure 3b), and n-
TiO2/CA/GCE (Figure 3c). The n-TiO2/CA/GCE gives a
high sensing current when compared to the CA/GCE and bare
GCE. The presence of TiO2 nanoparticles in the cellulose
acetate matrix leads to the shift of hydrogen evolution nearly by
200 mV more cathodic region, which improves the measure-
ment of true sensing current of chlorpyrifos. The peak observed
Figure 2. Effect of volume of nano-TiO2/cellulose acetate composite on bare GCE is close to the hydrogen evolution potential.
solution on the peak current of 50 μM chlorpyrifos in 60:40 (v/v)
Cellulose acetate is a negatively charged membrane, which is a
methanol/water containing 0.05 M TBAB at 100 mV s−1.
good matrix for the incorporation of TiO2 nanoparticles due to
the physical interaction of TiO2 nanoparticles with cellulose
acetate,29 which was confirmed by FT-IR analysis. Figure 4

Figure 3. Cyclic voltammograms of 50 μM chlorpyrifos at (a) bare

GCE, (b) cellulose acetate modified GCE, and (c) n-TiO2/CA/GCE
in 0.05 M TBAB 60:40 (v/v) methanol/water containing 0.05 M
TBAB at 100 mV s−1. Figure 4. FTIR spectra of (a) cellulose acetate, (b) nano-TiO2, and
(c) nano-TiO2/cellulose acetate composite.
GCE. The reduction peak is observed at around −1.55 V. This
peak is due to the electroreduction of −CN of the pyridine shows the FTIR spectra of the CA, nano-TiO2, and n-TiO2/CA
ring of the chlorpyrifos via a 2e− transfer step as reported composites. The peaks are identified as follows: The broad peak
earlier.11−13 at 3430 cm−1 is due to the −OH stretching frequencies. The
broad peak around 2900 cm−1 is due to the −C−H stretching
frequencies. The absorption peak around 1700 cm−1 is due to
the CO stretching frequencies.30,31 The −C−H bending
vibration peak around 904 cm−1 and the −OH out-of-plane
bending peak around 600 cm−1 are of low intensity in the
composite film (Figure 4c). The IR absorption peaks above
2000 cm−1 are intense and are composition dependent. All
three IR spectra show similar characteristics, which demon-
strates that the interaction between titania particles and
cellulose acetate film matrix is through physical adsorption
and not chemical bonding.
No peaks are observed on the reverse scan, which means that The presence of TiO2 in the cellulose acetate increases the
the reduction process is irreversible. The peak current increases sensing current of chlorpyrifos, which is due to the electro-
with the increase in the scan rates and the concentrations. A catalytic activity of TiO2 nanoparticles. The pores in the film
linear relationship between the peak currents and the square may also contribute to the increase in the peak currents. Figure
6152 DOI: 10.1021/acs.jafc.5b02057
J. Agric. Food Chem. 2015, 63, 6150−6156
Journal of Agricultural and Food Chemistry Article

5 shows the effect of various concentrations of chlorpyrifos on concentration of chlorpyrifos. The peak current varies linearly
the peak current of chlorpyrifos. The peak current increases with an increase in the concentration of chlorpyrifos from 20 to
110 μM (inset in Figure 6). The LOD and the LOQ values are
3.5 and 11.7 μM, respectively. The analytical parameters
obtained on various electrodes reported in the literature are
presented in Table 1. Although the reduction potential of
chlorpyrifos on nano-TiO2/cellulose acetate modified GCE is
higher than the values reported on mercury-based electrodes,
from an environmental point of view, mercury is not a suitable
material for sensing. The reduction potentials are comparable
with the PEDOT modified and carbon paste modified
electrodes. The nano-TiO2/cellulose acetate modified GCE
presented in this work is stable, reproducible, and biocompat-
ible and, moreover, the preparation of the modified electrode is
simple.
Amperometric Analysis. Figure 7 shows the ampero-
metric response of chlorpyrifos at nano-TiO2/cellulose acetate
modified GCE. It was recorded at a constant potential of −1.5
V. The reduction current increases for each addition of
chlorpyrifos, and the steady state current was measured. The
Figure 5. Influence of various concentrations of chlorpyrifos on the peak current varies linearly with the increase in concentration
peak current, (a) 10, (b) 30, (c) 50, (d) 70, (e) 90, (f) 110, of chlorpyrifos from 20 to 340 μM (inset in Figure 7). The
(g) 130 μM, at nano-TiO2/cellulose acetate modified GCE in 60:40 LOD and the LOQ values are 11.8 and 39.2 μM, respectively.
(v/v) methanol/water containing 0.05 M TBAB at 100 mV s−1. Reproducibility and Stability of n-TiO2/CA/GCE. The
(Inset) Calibration graph.
electrochemical responses are affected by the surface chemistry
of carbon−oxygen functionalities present on the GC electrode
with the increase in the concentrations of chlorpyrifos ranging and cleanliness, that is, the absence of adsorbed impurities.33−36
from 10 to 130 μM (inset graph in Figure 5). The limit of In the present work GC was hand polished with finer emery
detection (LOD) and limit of quantitation (LOQ) were papers to remove the oxide layers and adsorbed impurities on
calculated from the calibration graph constructed with the electrode surface. Then the GC electrode was throughouly
concentration of chlorpyrifos on the x-axis and reduction washed with Millipore water to remove the loosely adsorbed
current on the y-axis using the relationships LOD = 3s/m and particles on the GC surface. The GC electrode was further
LOQ = 10s/m, where s is the standard deviation of the chemically cleaned with NaOH, HNO3, and MeOH. The
intercept and m is the slope of the calibration curve.32 The electron transfer rates of redox reactions and reproducibility on
LOD is 4.4 μM, and the LOQ is 14.7 μM. the GC electrode are controlled by the distribution of surface
Differential Pulse Voltammetric Analysis. Typical DPV oxides. The distribution of surface oxides was modified by
curves at various concentrations of chlorpyrifos are shown in exposing the GC electrode to NaOH and HNO3. The surface
Figure 6. The peak current obtained after subtracting the
of GC contains COH and CO functional groups. The
background current increases with the increase in the
relative density of these species varies with the chemical
treatments with NaOH and HNO3. Treatment with NaOH
increases the surface coverage of COH and with HNO3
increases the surface coverage of CO. Methanol is a less
aggressive cleaning agent, which desorbs the solution
impurities.37,38 Bare GC electrodes pretreated by the above
methods gave reproducible voltammetric responses for the
ferrocyanide/ferricyanide redox system in 0.1 M KCl. Hence,
the above pretreatment procedures were adopted in the present
work.
First, the reproducibility of the bare GC electrode pretreated
with emery papers and chemical agents such as NaOH, HNO3,
and MeOH was established by recording the cyclic
voltammetric responses of ferricyanide/ferrocyanide in 0.1 M
KCl.26 The pretreatment procedures used in this work were
sufficient to give reproducible CV responses. The pretreated
GC electrode was used for modification with n-TiO2/CA
composite film. The modified GC electrode was potentiostati-
cally cycled from the rest potential to the hydrogen evolution
Figure 6. Differential pulse voltammetric response of various
potential at slow sweep rates, for example, 10 mV s−1 in
concentrations of chlorpyrifos, (a) 20, (b) 30, (c) 40, (d) 50, (e) supporting electrolyte solution. After a few cycles, the
80, and (f) 110 μM, at nano-TiO2/cellulose acetate modified GCE in background current was stable and reproducible. Then cyclic
60:40 (v/v) methanol/water containing 0.05 M TBAB. (Inset) voltammograms were recorded for the reduction of chlorpyrifos
Calibration graph. on n-TiO2/CA/GCE.
6153 DOI: 10.1021/acs.jafc.5b02057
J. Agric. Food Chem. 2015, 63, 6150−6156
Journal of Agricultural and Food Chemistry Article

Table 1. Comparison of Analytical Parameters on Various Modified Electrodes

method electrodea linear range LOD LOQ ref
DPASV HMDE (−1.2 V) 9.9 × 10−8−5.96 × 10−7 M 9.9 × 10−8 M 11
DPV HMDE (−1.2 V) (5.7−28.5) × 10−8 M 4.0 × 10−10 M 1.2 × 10−9 M 13
cyclic voltammetry PEDOT/GCE (−1.6 V) 10 × 10−10−7 × 10−7 M 8 × 10−10 M 15
DPP DME (−1.2 V) 9.7 × 10−7−6.9 × 10−6 M 8.7 × 10−7 M 12
DPAdSV CMCPE (−1.2 V) 2.8 × 10−10−5.7 × 10−6 M 2.2 × 10−10 M 14
cyclic voltammetry TiO2/CA/GCE (−1.5 V) (10.0− 30) × 10−6 M 4.4 × 10−6 M 14.7 × 10−6 M present work
DPV TiO2/CA/GCE (−1.5 V) (20.0−110) × 10−6 M 3.5 × 10−6 M 11.7 × 10−6 M present work
amperometry TiO2/CA/GCE (20.0−340) × 10−6 M 11.8 × 10−6 M 39.2 × 10−6 M present work
a
The value given in parentheses is the reduction potential.

Figure 7. Amperometric response of chlorpyrifos for the constant Figure 8. Stability of the n-TiO2/CA/GCE electrode over time for the
addition of 20 μM at nano-TiO2/cellulose acetate modified GCE in addition of 50 μM chlorpyrifos in 60:40 (v/v) methanol/water
60:40 (v/v) methanol/water containing 0.05 M TBAB. (Inset) containing 0.05 M TBAB at 100 mV s−1.
Calibration graph.
nitropesticides. The possible interference of chlorocompounds
Reproducibility of the electrochemical response of this such as chlorophenol, chloroaniline, and chlorobenzene was
electrode was checked by carrying out a series of seven also analyzed. The reduction of these chlorocompounds is not
repetitive experiments for the fixed concentration of 50 μM observed on this electrode under the present experimental
chlorpyrifos. The peak currents are reproducible with the conditions, and these chlorocompounds do not show any
relative standard deviation of 2.54%. The reproducible response interference in the sensing signal of chlorpyrifos (Figure 9).
of the modified electrode with respect to time was checked Real Sample Analysis. Chlorpyrifos-Spiked Water Anal-
(Figure 8). After the modification, the same electrode was used ysis. The analytical utility of the above methods was checked
for the sensing of chlorpyrifos for 15 days successively. The with the water sample, which was collected at the Central
peak currents are reproducible with the relative standard Electrochemical Research Institute (CECRI) premises. It was
deviation of 5.3%. The stability of the electrode was also tested for the presence of chlorpyrifos. Chlorpyrifos was absent
checked. After 40 cycles of cyclic voltammetric scans, the peak in the water sample. Therefore, a 100 μM concentration of
current variation from the initial current was 2.8% only. This chlorpyrifos was spiked into the water sample and was
shows that the nano-TiO2/cellulose acetate film is highly stable thoroughly shaken for 1 h. Then it was extracted by using
and reproducible. dichloromethane. A small amount of anhydrous sodium sulfate
Interference Study. The interference study of several was added to the extracted sample to remove traces of water.
inorganic species and pesticides on the reduction signal of 50 The solvent was slowly evaporated to get the residue. The
μM chlorpyrifos was carried out using cyclic voltammetry. The chlorpyrifos residue was dissolved in solvent supporting
concentration of the pesticides and the interfering ions were electrolyte and was used as analyte for electrochemical
taken in 1:1 ratio. The inorganic ions such as Ca2+, Mg2+, Na+, experiments. The recovery rates obtained in electrochemical
NH4+, and K+ do not interfere with the chlorpyrifos reduction techniques are summarized in Table 2. The results are
signal. Possible interferences with the other nitroaromatic compared with the HPLC method.
pesticides such as methyl parathion and fenitrothion were also Commercial Sample Analysis. The commercial chlorpyrifos
checked. These pesticides are reduced at around −700 mV on sample was analyzed using nano-TiO2/cellulose acetate
n-TiO2/CA/GCE, whereas chlorpyrifos is reduced at around modified GCE as a sensor probe. One hundred milliliters of
−1.55 V. The wide variation in the reduction potential makes it commercial chlorpyrifos was purchased from the local market,
possible to determine chlorpyrifos even in the presence of these which contains approximately 20% (v/v) chlorpyrifos. The
6154 DOI: 10.1021/acs.jafc.5b02057
J. Agric. Food Chem. 2015, 63, 6150−6156
Journal of Agricultural and Food Chemistry Article

sample was analyzed by electroanalytical techniques and HPLC

measurements. The numer obtained in HPLC measurements is
taken as reference value. The results obtained in electro-
chemical techniques are well comparable with the HPLC
techniques (Table 4), so the electrochemical sensor using this
nano-TiO2-cellulose acetate modified electrode is promising for
the analysis of environmental samples.

Table 4. Soil Sample Analysis

electroanalytical technique concn (μM)a,b
cyclic voltammetry 91.62 ± 0.31
differential pulse voltammetry 91.64 ± 0.23
amperometry 102 ± 0.12
HPLC 99.6 ± 0.08
a
Number of samples analyzed was 6. bTotal weight of the soil was
112.6 g.

Figure 9. Interference study of various inorganic metal ions and

pesticides on the reduction signal of 50 μM chlorpyrifos at n-TiO2/
In this study a stable, reproducible, and biocompatible nano-
CA/GCE in 60:40 (v/v) methanol/water containing 0.05 M TBAB at TiO2/cellulose acetate modified electrode was developed and
100 mV s−1. used for the analysis of chlorpyrifos. The presence of TiO2
nanoparticles increases the sensing current of chlorpyrifos,
Table 2. Recovery Study of Chlorpyrifos in Spiked Water which enhances the sensitivity of the sensor. Moreover, the
Samples presence of TiO2 nanoparticles in the cellulose acetate matrix
shifts the hydrogen evolution markedly, which improves the
amount added amount recovereda recovery measurement of true sensing current of chlorpyrifos. The
method (μM) (μM) ± SD rate (%)
modified electrode is highly stable with respect to time so that
cyclic voltammetry 100 91.84 ± 0.18 91.84 the electrode once modified can be used many times for the
differential pulse 100 96.28 ± 0.11 96.28 sensing of chlorpyrifos. The electrode modification procedure
voltammetry
amperometry 100 96.46 ± 0.01 96.46
outlined in this work is also simple. The nano-TiO2/cellulose
HPLC 100 98.80 ± 0.08 98.80
acetate film on the glassy carbon electrode surface is highly
a stable in alcoholic medium, which makes this physically mixed
Number of samples analyzed was 6.
composite material suitable for the determination of chlorpyr-
ifos in alcoholic medium. This modified electrode replaces the
actual concentration of the commercial samples was mercury sensing electrode in the determination of chlorpyrifos.
determined using an HPLC technique and was taken as The materials used in the preparation of the modified electrode
reference value. It was diluted to 100 μM. Then it was used as are cheap. The modified electrode can easily be renewed for
an analyte in cyclic voltammetry, differential pulse voltammetry, subsequent analysis. The analytical utility of the proposed
and amperometry to verify the concentrations specified by the method was checked in the spiked water sample and the
manufacturer. The concentration obtained in electroanalytical commercial sample.

■
techniques is given in Table 3. The results obtained with
electroanalytical techniques are comparable with the results AUTHOR INFORMATION
obtained in the HPLC method.
Corresponding Author
*(M.C.) Phone: +91 4565 241552. Fax: +91 4565 227779,
Table 3. Commercial Sample Analysis 227713. E-mail: [email protected].
method concn (%)a,b (v/v) Funding
cyclic voltammetry 17.5 ± 0.50 We thank the Department of Science and Technology, New
differential pulse voltammetry 18.00 ± 0.09 Delhi, India, for financial support. A.K. thanks the Council of
amperometry 16.5 ± 0.08 Scientific and Industrial Research (CSIR), New Delhi, India, for
HPLC 18.61 ± 0.10 awarding a Senior Research Fellowship (SRF).
a
Concentration specified by the manufacturer is approximately 20% Notes
(v/v). bNumber of samples assayed was 6. The authors declare no competing financial interest.

Soil Analysis. Ten milliliters of chlorpyrifos was taken from

the 100 mL commercial chlorpyrifos pack, which contains 20%
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Journal of Agricultural and Food Chemistry Article

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6156 DOI: 10.1021/acs.jafc.5b02057

J. Agric. Food Chem. 2015, 63, 6150−6156