Journal of Hazardous Materials 177 (2010) 1077–1084

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Journal of Hazardous Materials

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

Square wave voltammetric determination of methyl parathion using

ZrO2 -nanoparticles modified carbon paste electrode
H. Parham ∗ , N. Rahbar
Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz, Iran

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

Article history: A carbon paste electrode is modified with ZrO2 -nanoparticles and its application for square wave voltam-
Received 12 November 2009 metric (SWV) detection of methyl parathion, MP (organophosphate pesticide) is reported. The nano-ZrO2
Received in revised form 5 January 2010 shows a strong affinity toward the phosphate group on methyl parathion molecules, which provides
Accepted 5 January 2010
sensitivity and selectivity of the modified carbon paste electrode. Instrumental and chemical parameters
Available online 11 January 2010
influencing the voltammetric response are optimized for MP determination. Under optimum experimen-
tal conditions the peak current is linear to MP concentration over the range of 5.0–3000.0 ng mL−1 with
Keywords:
a correlation coefficient of 0.9992. The limit of detection (LOD) and limit of quantification (LOQ) for MP
Methyl parathion
ZrO2 -nanoparticles
based on three and ten times the standard deviation of the blank (3Sb , 10Sb ) were 2.0 and 5.7 ng mL−1
Modified carbon paste electrode (n = 20) for MP, respectively. The recovery values from quality control (QC) samples of water solutions con-
Square wave voltammetry taining low, middle and high concentrations of MP (50, 100 and 800 ng mL−1 ) were 98.0 ± 2.3%, 92.5 ± 4.9%
and 97.6 ± 2.8%, respectively. The electrode is successfully applied for the determination of MP in different
water samples.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction Pesticides and insecticides are used to protect agricultural crop

against damaging caused by insects. However, ecological compart-
Pesticides are chemicals specifically developed and produced ments such as lakes and rivers may be contaminated by these
for use in the control of agricultural and public health pests, to chemicals through rains and wind, affecting many other organisms
increase production of food and fiber, and to facilitate modern agri- away from the first target. Only 0.1% reaches the specific target [4,5].
cultural methods. They are usually classified according to the type Fig. 1 shows the structure of methyl parathion as an organophos-
of pests (fungicides, algicides, herbicides, insecticides, nematicides, phorous pesticide (OPs) largely used in many countries to avoid
and molluscicides) that are used to control food and fiber produc- agriculture losses due to fruit flies, bugs, and other insect attacks.
tion. When the word ‘pesticide’ is used without modification, it Pesticides and insecticides are chemical pollutants to aquatic envi-
implies a material synthesized by humans. ronments. Fishes are able to bio-accumulate these pollutants due
Pesticides are a group of most important chemical pollutants to direct exposure or ingestion of contaminated preys and foods
that need to be more heavily monitored due to their toxicity, per- [4]. Methyl parathion is classified, due to its chemical structure, as
sistence, accumulation in the environment and their effects on the an ester of thiophosphoric acid. It may be converted in vivo into
environment and health [1,2]. The manufacture of pesticides is a the active metabolite, methyl-paraoxon, which acts as an acetyl-
multi-billion dollar industry. The United States is one of the great- cholinesterase inhibitor, causing accumulation of acetylcholine at
est manufacturers of pesticides and herbicides and has an annual nerve endings in the peripheral or central nervous system. In ani-
market of over USD 10 billion per annum. If pesticides were not mals, methyl parathion is absorbed at a high rate and is also
used, it is estimated that one third of the world’s food crops would eliminated very quickly. The elimination takes place predominantly
be destroyed by pests either during growth, harvesting, or stor- via the renal route, supported by the finding that the highest con-
age. Losses would be even higher in developing countries [1]. At centrations of residues were found in the kidney. Because of the
the same time, according to the European Union Directive, indi- high toxicity, bio-accumulation effect and long-term damage to the
vidual pesticide in drinking water must not exceed 0.1 ng mL−1 for environment and animal lives even at very low concentration [6,7],
individual compound and some of its degradation products, and the quantitative detection of organophosphate pesticides is quite
0.5 ng mL−1 for the sum of all compounds [3]. significant.
Many efforts have been made to develop sensitive, convenient
and effective methods for pesticide residue analysis in environ-
∗ Corresponding author. Tel.: +98 611 3360018; fax: +98 611 3337009. mental samples. Complicated traditional methods of analysis such
E-mail address: hoparham@yahoo.com (H. Parham). as gas or liquid chromatography, mass spectroscopy and high-

0304-3894/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2010.01.031
1078 H. Parham, N. Rahbar / Journal of Hazardous Materials 177 (2010) 1077–1084

that the nano-ZrO2 carbon paste electrode has excellent sensing

performance toward parathion as a representative MP molecule,
including high sensitivity and selectivity, rapid regeneration, con-
venient fabrication, low-cost production, easy control of electrode
area and shape. The electrochemical characteristics of the new
Fig. 1. The structure of methyl parathion (MP).
electrode and its application for quantitative analysis of MP were
evaluated using cyclic voltammetry and square wave voltammetric
methods.
performance liquid chromatography (HPLC) have been widely used The main objectives of this nano-ZrO2 -modified carbon paste
for the determination of Ops [8–12]. However, these methods electrode for MP detection are: wide linear dynamic range
suffer from expensive and extensive pre-treatment steps, using (5.0–3000.0 ng mL−1 ) and low LOD of the method (2.0 ng mL−1 )
toxic organic solvent and also long analysis time. These disadvan- which are better than some of the previously reported methods
tages limit the application of such methods primarily to laboratory [12,18,20,23,26,28,29,31]. No use of toxic Hg electrode, and short
settings and prohibit their use for rapid analysis under field condi- time of the procedure (total time of a single determination is about
tions. 10 min) are also some more advantages of the developed method.
Quantitative detection of some pesticides and insecticides Although, some chromatographic and biosensing methods show
using electrochemical biosensors based on enzyme activities has better LOD than that of the developed method, but these meth-
emerged the past few years as the most promising alterna- ods suffer from extensive and expensive pre-treatment steps and
tive to detect pesticides. Among these electrochemical methods, lengthy time of analysis. The developed method shows good and
acetylcholinesterase (AChE) biosensors based on the inhibition comparable recovery percent values (98.8–102.0) with respect to
on AChE have shown satisfactory results (low detection lim- other reported methods.
its) for pesticides analysis [13–21]. But, these methods suffer
from extensive pre-treatment steps and lengthy time of analy- 2. Experimental
sis.
More than 70% of pesticides used over the entire world are 2.1. Reagents and solutions
of organophosphate pesticides’ (OPs) types and their derivatives.
The pesticides containing nitro-phenyl groups or halogens, are All chemicals were of analytical grades and obtained from Merck
electrochemically active compounds and thus very suitable for (Darmstadt, Hesse, Germany). methyl parathion (MP) was pur-
electrochemical detection. Pesticides such as methyl parathion chased from Fluka (Milwaukee, USA). Graphite powder (with a
(MP), paraoxon and fenitrothion (some nitroaromatic OP com- size <100 ␮m) was purchased from Fluka (Milwaukee, USA). Zir-
pounds), exhibit good redox activities at the electrode surface [22]. conia (ZrO2 , 30–60 nm) was purchased from Inframat Advanced
Recently, more attentions have been given to their inherent elec- Materials (Farmington, CT, USA). Double distilled water was used
trochemical activity on solid electrode and the compact nature of throughout.
electrochemical instruments [23,24]. Methyl parathion (MP) stock solution (100 ␮g mL−1 ) was pre-
Electrochemical methods can provide quantitative detection pared by dissolving 0.0100 g of MP separately in 15 mL of ethanol
of pesticides with a lower cost, short analysis time and can be and diluting to 100 mL with distilled water in a 100 mL volumetric
easily miniaturized and integrated with respect to those meth- flask. Working solutions were prepared by appropriate dilution of
ods described above. Voltammetric detection methods have been the stock solution with distilled water.
widely used in many fields such as biomedicine, environmental sci-
ence, and food analysis. However, there are many reports on direct
voltammetric pesticides determination because of their simplicity, 2.2. Apparatus
convenience, rapidness, sensitivity and accuracy. So these meth-
ods have drawn more and more attention for OP residue analysis. All voltammetric measurements were carried out on an EG &
Mercury electrode is used as the working electrode for pesticide G 273A electrochemical device (Princeton Applied Research, PCR,
microanalysis [25,26]. The use of mercury based electrodes is now USA). Adjustment of pH was carried out using a pH-meter (632
rather unwanted and most of the studies have been focused on Metrohm, Herisau, Switzerland). A Pentium 4 computer controlled
fabrication and modification of different working electrodes to all settings and data processing of the system.
improve their sensitivity and lower the detection limit [27–35]. A three-electrode arrangement was used throughout. A ZrO2 -
Specific enzymes, organic compounds with electrochemical activ- nanoparticle modified carbon paste acts as working electrode and
ity, and nano-materials are usually employed as the modifying a platinum wire was used as auxiliary electrode together with an
materials. Although these methods were accurate; the great draw- Ag/AgCl reference electrode, using 3 M KCl as electrolyte with a
back came from electrode surface renewal by tedious mechanical porous membrane.
polishing.
Modification of carbon paste electrodes using nano-materials, 2.3. Fabrication of the ZrO2 modified carbon paste electrodes
can greatly improve the physical characteristics of the fabricated
sensors, such as their sensitivity, angular rigidity, abrasion resis- Carbon paste electrodes (CPE) were prepared by mixing 70%
tance and causticity resistance with respect to non-modified carbon graphite powder with 30% paraffin oil for 5 min (ratio of C:Paraffin,
paste electrodes. However, there are few reports on fabrication and 70:30, w/w). ZrO2 -nanoparticle (modifier) was added to the paste
application of non-modified and modified carbon paste electrodes and mixed on mortar for at least 20 min to produce the final mod-
for MP detection [23,24,31,34]. In most of the reported electroana- ified carbon paste electrode (MCPE). So, the composition of each
lytical methods non-modified carbon paste electrodes show less electrode contains 5:70:30 weight ratio of ZrO2 :C:Paraffin. The
sensitive signals for detection of analyte with respect to modi- MCPE was finally obtained by packing the paste into an insulin
fied carbon paste electrodes. In this paper the characteristics of syringe and arranged with a copper wire serving as an external
a nano-ZrO2 -carbon paste electrode based on the high surface electric contact. Appropriate packing was achieved by pressing the
area of zirconia nanoparticles and their selective affinity for phos- electrode surface against a weighing paper until a smooth surface
phate groups are reported [33]. The experimental results showed was obtained.
 H. Parham, N. Rahbar / Journal of Hazardous Materials 177 (2010) 1077–1084 1079

2.4. Voltammetric detection of methyl parathion

Methyl parathion (MP) is an OP and showed good voltam-

metric signal in the presence of solid electrodes modified with
different materials including ZrO2 [27–35]. The general proce-
dure adopted for obtaining square wave voltammograms of MP
was as follows: 2.0 mL of acetate buffer solution (pH 5.25) and
appropriate amount of standard MP solutions (final concentration
of MP was ranged between 5.00 and 3000.00 ng mL) were added
into a 10 mL volumetric flask. Then the solution was diluted to
the mark with distilled water and transferred into the electro-
chemical cell. The ZrO2 modified carbon paste electrode (MCPE)
with reference and auxiliary electrodes were dipped into the test
solution and then nitrogen gas was purged for 3 min in open-
circuit. Square wave voltammograms were recorded by applying
a negative-going potential scan over the range of +0.50 to −0.50 V, Fig. 2. Cyclic voltammograms of MP on (a) non-modified and (b) modified carbon
with a pulse height potential of 25 mV, and a frequency of 60 Hz. paste electrode. [Conditions: concentration of MP: 3.0 ␮g mL−1 ; pH 5.0; accumula-
In order to regenerate new and fresh surface on MCPE, the tion time: 5 min; conditioning potential: −1.0 V].
tip of the electrode was polished against a weighing paper for
2 min. 3. Results and discussion
In the case for water samples, 2 mL of buffer solution was added
to 8 mL of water sample and the mixture is transferred to elec- 3.1. Electrochemical characteristics of methyl parathion on MCPE
trochemical cell and the recommended procedure is followed as
mentioned above. Early cyclic voltammetry studies on electrochemical behavior of
10 ␮g mL−1 of methyl parathion (MP) that we have carried out on
both non-modified and modified carbon paste electrodes showed
2.5. Method validation that the voltammograms of adsorbed MP on these two electrode
surfaces in acetate buffer (pH 5.25) media differ significantly. Fig. 2
The method was validated for linearity, precision, accuracy shows the voltammograms of MP on the non-modified (Fig. 2a)
and selectivity according to the US- Food and Drug Administra- and modified carbon paste electrode (Fig. 2b). As it is seen the
tion (US-FDA) guideline for validation of bio-analytical methods voltammogram of MP on non-modified electrode shows low sen-
[36]. Validation runs were conducted for five consecutive days. sitivity with respect to organophosphate pesticides (OPs) such as
The peak current intensity measurements of analyte solution con- MP. But the voltammogram of MP on the ZrO2 modified carbon
taining the quality control (QC) amounts of MP were interpolated paste electrode (MCPE) shows a well-defined peak current which
from the calibration curve on the same day to give concentra- indicates the efficient adsorption of MP due to presence of ZrO2 -
tions of the analyte. The results from QC samples in six runs nanoparticles in the paste. Well-defined redox peaks (EPa , −0.10 V
were used to evaluate the precision and accuracy of the devel- and EPc , −0.22 V) and irreversible reduction peak (EPc , −0.80 V)
oped method. The calibration curve of MP was constructed using were observed in the potential range from +0.50 to −1.0 V (Fig. 2b).
standard sample solutions at nine concentrations in the range The irreversible reduction peak at −0.80 V corresponds to the
of 5.0–3000.0 ng mL−1 of MP with least squares linear regression reduction of the nitro group to hydroxylamine group, reaction (I),
method. The limit of quantification (LOQ) is defined as the lowest and the two redox peaks at −0.10 and −0.22 V are attributed to two-
concentration on the calibration curve at which an acceptable accu- electron-transfer process, reactions (II) and (III), as shown below.
racy within ±20% and a relative standard deviation (RSD) below 20% This mechanism is consistent with those described elsewhere for
can be obtained. OP pesticides and nitroaromatic compounds [37–39].

(I)

(II)

(III)
In order to test the reproducibility and repeatability of the pro- The sensitive square wave voltammetric (SWV) method is cho-
posed method, the intra-day precision and accuracy were evaluated sen to determine trace quantities of MP in different water samples.
by determining a replicate analysis of QC samples of MP on the same Fig. 3 shows a sharp, symmetric and well-defined SW voltam-
day. The run consisted of a calibration curve and four replicates of mogram peak of MP (3 ␮g mL−1 ) which is obtained between the
each low, middle, and high concentration quality control samples. potential range from +0.30 to −0.30 V in acetate buffer (pH 5.25).
For determining the inter-day accuracy and precision, analyses of The maximum SW peak current of the MP occurs at −0.028 V.
three batches of QC samples were performed on different days. The In order to obtain a well-defined peak with maximum peak
selectivity was evaluated by comparing the peak current intensity current for the determination of trace amounts of MP, different
changes for accumulated MP at the electrode surface in different chemical and instrumental parameters such as electrode com-
batches containing different interfering species. position weight ratios, pH, buffer volume, accumulation time,
1080 H. Parham, N. Rahbar / Journal of Hazardous Materials 177 (2010) 1077–1084

by weight show low conductivity and so no voltammogram was

obtained in such cases. In the cases where the paraffin ratio is less
than 30%, the paste becomes dry (polishing process is hard and
takes a long time) and no good voltammogram was obtained in
these cases. In further experiment the paste with a weight ratio of
70:30 (C:Paraffin) was used thoroughly.
ZrO2 -nanoparticles were used for modification of the paste.
Different amounts of ZrO2 -nanoparticles were added to 10.0 g
of paste (70:30, w/w) and mixed thoroughly on mortar for at
least 20 min to produce the final paste for electrode prepara-
tion. Fig. 4 shows the peak current values obtained for different
weight ratios of ZrO2 :C:Paraffin. Highest peak current was shown
by ZrO2 :C:Paraffin weight ratio of 5:70:30 and this weight compo-
sition was used for MCPE construction in further works. In cases of
lower ratios than 5 for ZrO2, the intensity of peak current decreases
due to lower amount of ZrO2 and low accumulation of MP on the
electrode surface. Higher amounts of ZrO2 (>5 g per 100 g of paste)
cause broadening of voltammogram which decreases the intensity
of peak current.
Fig. 3. The SW voltammogram of MP on modified carbon paste electrode vs Ag/AgCl
reference electrode. [Conditions: concentration of MP: 3.0 ␮g mL−1 ; pH 5.0; accu-
mulation time: 5 min; conditioning potential: −1.0 V; conditioning time: 12 s; pulse
3.3. The effect of pH
height: 25 mV; scan increment: 2 mV; frequency: 60 Hz.].
The effect of pH of the test solution on the peak current of
MP voltammograms was studied by applying Britton–Robinson,
accumulation potential, equilibration time (ET), pulse height, fre- phosphate and acetate buffer solutions. Among the various inves-
quency and scan increment were optimized using one variable at tigated buffers in the pH range of 3.0–8.0, the best voltammetric
the time procedure. In the investigation process, each variable was signal in terms of sensitivity (peak height) was obtained at pH
changed while the others were kept constant. Preliminary exper- 5.25 using acetate buffer. The optimum volume of the buffer
iments carried out with two levels full factorial designs showed solution was found to be 2 mL as shown in Fig. 5. At pH val-
that there is no significant interaction between significant param- ues lower than 5, the reduction of hydronium ion (H3 O+ ) may
eters such as pH and amount of ZrO2 -nanoparticles; accumulation cause the decrease in intensity of peak current. At pH values
time and conditioning potential. Therefore, these parameters were greater than 5.5 the decomposition of MP causes sensitivity reduc-
optimized by the one-factor at a time method. tion.

3.2. Electrode composition

3.4. The type of supporting electrolyte
In order to obtain the most sensitive and best weight ratio (w/w)
of C:Paraffin oil for preparation of paste electrode, different weight The effect of different salt solutions (as supporting electrolyte)
compositions (90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40 and on SW voltammogram of MP was investigated. Sample solu-
55:45) of graphite:paraffin were mixed thoroughly to get a homo- tions containing salts such as KCl, KNO3 , NaCl and K2 SO4 in the
geneous paste. The constructed pastes were used to obtain cyclic concentration range of 0.0–0.2 mol L−1 were tested. The results
voltammogram from MP and the best voltammogram was obtained revealed that the peak current and sensitivity of the method do not
by 70:30 (w/w) ratio. Mixtures with paraffin ratios more than 30% change significantly with type and salt concentration. Thus, fur-
ther works were performed without addition of any electrolyte
solution. Acetate buffer also acts the role of supporting elec-
trolyte.

Fig. 4. The effect of the amount of ZrO2 -nanoparticles per 100 g of carbon paste
(C:Paraffin, 70:30, w/w) on the peak current intensity (−0.028 V) of MP voltammo- Fig. 5. The effect of pH of sample solution on the peak current intensity (−0.028 V)
gram. [Conditions: concentration of MP: 0.5 ␮g mL−1 ; pH 5.0; other variables are of MP voltammogram. [Conditions: same as those in Fig. 4, except that the pH of
same as those in Fig. 3.]. sample solution is variable.].
 H. Parham, N. Rahbar / Journal of Hazardous Materials 177 (2010) 1077–1084 1081

Fig. 6. The effect of accumulation time on the peak current intensity (−0.028 V) of
MP voltammogram. [Conditions: pH 5.25; other variables are same as those in Fig. 4, Fig. 7. The effect of conditioning potential on the peak current intensity (−0.028 V)
except that accumulation time is variable.]. of MP voltammogram. [Conditions: accumulation time: 3 min; other variables are
same as those in Fig. 4, except that conditioning potential is variable.].

3.5. The effect of equilibration time (ET) and scan increment (SI)
on MP voltammograms nature of MP under this condition. Thus, an accumulation is per-
formed under open-circuit.
Equilibration time (ET), which controls a variable delay dur-
ing the cell performance, was studied. Equilibration times of 0,
5, 10, 15, 20, 25 and 30 s were applied to the electrodes and 3.9. Influence of conditioning potential and conditioning time
the corresponding voltammograms were recorded. The results
showed no measurable increase in peak current at ET values greater In order to prepare the conditions for electrochemical reac-
than 0 s. Thus, a time period of 0 s was selected as optimum ET tion of the analyte (MP) at the electrode surface, a conditioning
value. potential must be applied to the working electrode. This poten-
The effect of scan increment, which determines the amount of tial must be applied to the electrode before potential scanning
potential changes between two data points in the experiment, was and recording the voltammograms for analytical purposes. As it
investigated. Scan increment values in the range of 1–10 mV (with is seen in Section 3.1, the reactant of reaction (II) is the product
1 mV intervals) were applied to the electrodes and the correspond- of reaction (I). The reversible redox pair (reactions (II) and (III))
ing voltammograms were recorded. The resulting peak currents will produce the SW voltammogram and this is due to occurrence
showed that, by increasing the scan increment up to 2 mV values, of reaction (I) at working electrode before any SW potential scan-
the voltammograms’ peak current will also increase steadily; so ning. Reaction (I) occurs by applying a conditioning potential after
2 mV was chosen as the optimum scan increment. accumulation of MP on the modified carbon paste electrode (MCPE)
surface under open-circuit. Different conditioning potentials were
applied in the range between 0.0 and −1.0 V. The results in Fig. 7
3.6. The effect of frequency on MP square wave voltammograms
show that at applied potentials smaller than −0.6 V, no considerable
peak current intensity was observed at −0.028 V (the peak poten-
The effect of frequency changes on the voltammograms peak
tial of methyl parathion (MP) SW voltammogram). The peak current
current (−0.028 V) of MP was studied between the range of
intensity of MP increases with increasing the applied potential to
20–200 Hz and the results showed that frequencies in the range of
−0.8 V and remains almost constant after this potential. The applied
40–80 Hz give the highest peak currents and so, 60 Hz was chosen
potential of −0.8 V was used throughout as the optimum condition-
as optimum frequency value.
ing potential for detection of MP. This potential matches with the
irreversible reduction peak (EPc , −0.80 V) that is observed in Fig. 2b.
3.7. The effect of pulse height
In order to obtain the optimum conditioning time, the conditioning
potential (−0.8 V) was applied in different time periods between 1
The effect of pulse height variation on the peak current of
and 14 s. The peak current intensity of MP increases with increas-
MP voltammograms was studied in the range of 15–125 mV. The
ing the conditioning time up to 10 s and remains almost constant
obtained results showed that increasing the pulse heights up to
after this time. Based on the obtained results, 10 s was chosen as
25 mV will cause an increase in peak current. Pulse heights more
optimum conditioning time.
than 25 mV cause broadening of the MP voltammogram and so
decreasing the peak current intensity of the analyte. So the opti-
mum pulse height value was selected to be 25 mV. 3.10. Effect of interfering ions

3.8. Influence of accumulation time and accumulation potential Prior to the application of proposed method on real samples it
was vital to investigate the effect of some of the interfering ions on
The SW peak current of MP increases with accumulation time the recovery percentage of MP. The SW voltammetric determina-
increasing from 0 to 180 s, as shown in Fig. 6. But when it exceeds tion of MP was tested in the presence of spiked known amounts of
180 s (3 min) the peak current remains almost constant for a interfering ions and molecules. The tolerance limit was defined as
0.5 ␮g mL−1 MP solution, meaning that an accumulation/or extrac- the amount of the foreign substance causing a change of ±5% in the
tion equilibrium is achieved at the electrode/solution interface. peak current intensity reading. The tolerable limits of interfering
The influence of accumulation potential is examined from +0.3 to substance are given in Table 1. The results showed that most of the
−0.5 V. The results showed that the peak current of MP is almost investigated substances do not interfere in the SW voltammetric
independent of accumulation potential. This is due to the neutral determination of MP in water samples.
1082 H. Parham, N. Rahbar / Journal of Hazardous Materials 177 (2010) 1077–1084

Table 1 Table 2
The tolerance limit of interfering substances on SW voltammetric determination Precision and accuracy data for SW voltammetric detection of MP in water sample
of MP (0.50 ␮g mL−1 ) using MCPE. [Conditions: pH 5.25; 2 mL of acetate buffer; using MCPE (intra-day: n = 6; inter-day: n = 6 runs per day, 5 days).
accumulation time: 3 min; conditioning potential: −0.80 V; conditioning time: 10 s;
pulse height: 25 mV; scan increment: 2 mV; frequency: 60 Hz.]. MP concentration (␮g mL−1 ) RSD (%) Relative error (%)

Substance Tolerance limit (␮g mL −1

) Added Found (mean ± S.D.) Intra-day Inter-day

K+ , Na+ , NH4 + , NO3 − 1500 0.050 0.049 ± 0.007 4.5 8.9 −2.0
SO4 2− , Cl− 1000 0.200 0.215 ± 0.014 3.7 6. 6 +7.5
Ca2+ , Mg2+ 100 0.800 0.781 ± 0.042 3.2 7.8 −2.4
Ni2+ , Co2+ , Fe2+ , Fe3+ 50
Hg2+ , Cr3+ , Pb2+ , Cd2+ 10
Cu2+ 5 Table 3
Nitrophenol, phenol 20 Determination of MP content and recovery test of MP in tap (100 mL) and river
(100 mL) water samples with the proposed method (n = 6). [Conditions: pH 5.25;
2 mL of acetate buffer; accumulation time: 3 min; conditioning potential: −0.80 V;
conditioning time: 10 s; pulse height: 25 mV; scan increment: 2 mV; frequency:
3.11. Analytical performance and method validation 60 Hz.].

Sample Added MP (␮g mL−1 ) Found MPa (␮g mL−1 ) Recovery (%)
In order to show the validation of the proposed method, the b d
Tap water – ND –
analytical features of the method such as linear range of the cal-
Tap water 0.050 0.051 ± 0.003 102.0
ibration curve, LOD, LOQ, accuracy and precision were examined. Tap water 0.100 0.097 ± 0.012 97.0
Fig. 8 shows the voltammograms of MP in the concentration range Tap water 0.800 0.789 ± 0.020 98.8
of 5.0–3000.0 ng mL−1 . Under the optimum conditions, the cal- River waterc – 0.051 –
River water 0.050 0.097 ± 0.005 94.0
ibration graph for the determination of MP is obtained with a
River water 0.100 0.146 ± 0.015 96.0
correlation coefficient of 0.9992. The regression equation for the River water 0.800 0.866 ± 0.021 102.0
line was i = 1.3641CMP + 0.6031 (n = 9), where CMP is the concen- a
x ± s (n = 6).
tration of MP in ␮g mL−1 and (i) is the peak current intensity b
Tap water components: Ca2+ = 52; Mg2+ = 29; Na+ = 37; CO3 2− = 61; Cl− = 24;
difference (at the peak potential −0.028 V) between the analyte SO4 2− = 25; NO3 − = 9 ␮g mL−1 ; pH 7.3; EC = 853.
and the blank voltammograms (Fig. 8). The slope of the line c
River water main components: Ca2+ = 82; Mg2+ = 49; Na+ = 68; CO3 2− = 91;
b = 1.3641 ± 0.0437 which shows a R.S.D. = 3.0% and the intercept of Cl− = 44; SO4 2− = 35; NO3 − = 9 ␮g mL−1 ; pH 7.1; TDS = 387; EC = 1340.
d
Not detected.
the line a = 0.6031 ± 0.004 with a R.S.D. = 4.6% were also obtained.
Under optimum experimental conditions, the LOD and LOQ, of the
proposed method based on three and ten times the standard devi- The recovery values from QC samples of water solutions con-
ation of the blank (3Sb , 10Sb ) [40] were 2.0 and 5.7 ng mL−1 for MP taining low, middle and high concentrations of MP (50, 100 and
(n = 9), respectively. 800 ng mL−1 ) were 98.0 ± 2.3%, 92.5 ± 4.9% and 97.6 ± 2.8%, respec-
Intra- and inter-day precision and accuracy data (showing tively.
reproducibility and repeatability terms) for SW voltammetric
detection of MP in QC samples are summarized in Table 2. The preci- 3.12. Application on real sample
sion and accuracy of the present method conform to the criteria for
the analysis of water samples according to the guidance of US-FDA In order to test the validity of the method, the proposed pro-
where the RSD determined at each concentration level is required cedure was applied for determination of MP in water samples.
not to exceed 15% (20% for LOQ) and R.E. within ±15% (±20% for Recovery tests were used to examine the reliability and accuracy
LOQ) of the actual value [40]. of the method, different amounts of MP were spiked into the tap
(100 mL) and river (100 mL) water samples and MP content of each
sample was determined at optimum conditions. The MP content
of different samples and recoveries of added analyte were evalu-
ated and the results showed that it is possible to determine the MP
concentration in real sample solutions using the proposed method
outlined in this investigation (Table 3).

4. Conclusion

The developed methodology of this study was simple, fast,

sensitive and cheap, especially if more sophisticated techniques
such as spectrofluorometry or chromatography are not available.
In addition, it is notable that up to our best knowledge this may
be the first modified carbon paste electrode used for MP detec-
tion. LOD of the method (2.0 ng mL−1 ) is better than some of the
previously reported methods [12,18,20,23,26,28,29,31]. The linear
dynamic range (5.0–3000.0 ng mL−1 ) of the developed method is
wider than all reported methods. The developed method was suc-
cessfully applied for determination of MP in water samples. No use
of toxic Hg electrode, short time of the procedure (total time of a
single determination is about 10 min) and low LOD are the main
advantages of the developed method. Table 4 shows a compari-
son of the proposed method with other reported methods. Some
Fig. 8. SW voltammograms of different concentrations of MP under optimum con-
ditions. (1) 0.0, (2) 5.0, (3) 10.0, (4) 20.0 (5) 50.0, (6) 100.0, (7) 500.0, (8) 1000.0, (9) reported LOD values [8–10,14,32–34] (most of these reports are
2000.0, and (10) 3000.0 ng mL−1 . chromatographic and biosensing methods) are better than that of
 H. Parham, N. Rahbar / Journal of Hazardous Materials 177 (2010) 1077–1084 1083

Table 4
The comparison of the proposed method (SW voltammetric determination of MP by ZrO2 -MCPE) with other reported methods of MP or other pesticides determination.

Detection methoda Detection limit (ng mL−1 ) Analysis time (min) Linear dynamic range (ng mL−1 ) Accuracy (%) Ref.
b b
GC (MP) 1.5 40 NR NR [8]
GC (MP) 0.08 >25 NR ±8 [9]
GC-MS (PS) 0.20 30 NR ±5 [10]
HPLC-FL (PS) 4–12 30 16–700 ±5 [12]
BIOS (PS) 0.0002 >30 NR ±7 [14]
BIOS (PS) 20 >60 NR ±10 [18]
BIOS (PS) 10 >30 1–20 ±20 [20]
V (MP) 100 >15 20–120 (␮g mL−1 ) NR [23]
V (MP) 4.8 >15 10–120 ±6 [26]
V (MP) 20 >40 20–700 ±10 [28]
V (MP) 100 >25 NR NR [29]
V (MP) 3 >15 20–140 ±5 [31]
V (MP) 1.2 >15 3–100 ±3 [32]
V (MP) 1.0 >25 3–2000 ±5 [33]
V (MP) 2.0 10 5–3000 ±5 Proposed
a
Gas chromatography (GC), gas chromatography–mass spectrometry (GC-MS), high-performance liquid chromatography–mass spectrometry (HPLC-MS), high-
performance liquid chromatography–mass Fluorimetry (HPLC-FL), biosensor (BIOS), and voltammetric (V).
b
NR, not reported.

the developed method, but these methods suffer from extensive tion I. Modification of carbon surface for immobilization of acetyl-
and expensive pre-treatment steps and lengthy time of analysis. cholinesterase, Biosens. Bioelectron. 20 (2004) 1118–1125.
[14] S. Sotiropoulou, N.A. Chaniotakis, Lowering the detection limit of the acetyl-
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acetylcholinesterase-based biosensor for attomolar detection of dichlorvos,
Acknowledgement Biosens. Bioelectron. 20 (2005) 2347–2352.
[16] J. Gong, L. Wang, L. Zhang, Electrochemical biosensing of methyl parathion
pesticide based on acetylcholinesterase immobilized onto Au–polypyrrole
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Council for financial support of this work (grant 1386). 2285–2288.
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