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Determination of Dinotefuran and Thiamethoxam Residues in PepperFruits

under Greenhouse Conditions using the QuEChERS Method and HPLC/DAD

Article in Egyptian Journal of Chemistry · April 2018

DOI: 10.21608/ejchem.2018.2803.1227

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23 Egypt. J. Chem. Vol. 61, No. 2, pp. 249 - 257 (2018)

Determination of Dinotefuran and Thiamethoxam Residues in

Pepper Fruits under Greenhouse Conditions using the QuEChERS
Method and HPLC/DAD
M. M. Rabea1, E. S. Ibrahim1, D. Elhafny2 and M. A. Bayoumi1*
1
Department of Economic Entomology and Pesticides, Faculty of Agriculture, Cairo
University, Egypt.
2
Pesticides Residues and Environmental Pollution Dept., Central Agricultural
Pesticides Laboratory, Agricultural Research Center, Giza, Egypt.

D ETERMINATION of dinotefuran and thiamethoxam residues levels in pepper samples

which were collected randomly at 0, 1, 3, 5, 7, 10, 15 and 21 days after treatment using
quick, easy, cheap, effective, rugged, safe (QuEChERS) method and clean up step utilizing solid-
phase extraction (SPE) followed by determination by high-performance liquid chromatography
with diode-array detection (HPLC/DAD). Dinotefuran and thiamethoxam were recovered
within 77-80% and 78-112%, respectively at the spike levels (0.01 - 1 mg/kg) in pepper
samples with relative standard deviations (RSDs) lower than 3%. Good linearity was achieved
for dinotefuran and thiamethoxam with an excellent correlation coefficient of R2 > 0.996 and
the matrix matched calibration also showed good linearity with determination coefficients R2 >
0.98. The initial deposits of dinotefuran and thiamethoxam in pepper fruits were 6.59 and 1.38
mg/kg, respectively. The half-life period (RL50) of tested pesticides on pepper fruits were 2 and
3.11 days for dinotefuran and thiamethoxam, respectively. According to maximum residue level
(MRL) (0.01 mg/kg for dinotefuran and 0.7 mg/kg for thiamethoxam) the pre-harvest interval
(PHI) was 11 and 4 days, respectively.
Keywords: Dissipation, Determination QuEChERS, Dinotefuran, Thiamethoxam, HPLC-DAD
and Pepper.

Introduction residues have been established by The United

States EPA in the range 0.02–6 mg kg-1 in different
Neonicotinoid insecticides including imidacloprid,
types of vegetables and fruits depending on the
acetamiprid, thiacloprid, thiamethoxam, clothianidin,
different pesticides and matrixes (http://www.
and dinotefuran are effective insecticides to control
mrldatabase.com).
pest with novel modes of action [1].
The evaluation of pesticide residues in food
Pesticides are widely applied to vegetables
matrices is a tremendous challenge mainly because
and fruits to guarantee their quality and to fulfill
the amounts of analytes are small compared to the
the consumer’s requirements and for the trade.
huge quantities of interfering substances which
However, these compounds can be unsafe for
strongly interact with analytes[3]. QuEChERS
humans, according to the levels of pesticides
has been developed as a new sample preparation
present. So, the European Union Council
methodology between 2000 and 2002 for pesticide
Directive 91/414/EEC controlled the maximum
multiresidue analysis[4]. Generic extraction
concentrations of these molecules [2]. On the
procedures, like QuEChERS method and ultra-
other hand, MRLs for neonicotinoid insecticides
high-performance liquid chromatography systems
*Corresponding author e-mail: mohammedabdallah851@agr.cu.edu.eg
DOI: 10.21608/ejchem.2018.2803.1227
©2017 National Information and Documentation Centre (NIDOC)
 250 M. M. RABEA et al.

combined with polar embedded C18 phases, Materials and methods

providing excellent peak shape and good resolution,
Materials
enabled us to detect a wide spectrum of compounds
Chemicals and reagents
which belong to different pesticides classes and
Certified reference standard of thiamethoxam
chemical properties in each sample[4, 5].
and dinotefuran (Fig. 1) > 98% purity was
Acetone, ethyl-acetate, methanol and acetonitrile- obtained from Central Agricultural Pesticides
based sample extraction techniques are generally Laboratory (CAPL). Acetonitrile of HPLC
used for multi-class pesticides which are typically grade was purchased from Merck. Bulk primary
followed by a clean-up step [6]. Several methods secondary amine (PSA) sorbent (Bondesil-PSA,
have been reported for the analysis of neonicotinoids 40 μm) was bought from Subelco. Anhydrous
(thiamethoxam, imidacloprid, and acetamiprid), for magnesium sulfate and sodium chloride were
example, HPLC coupled with ultraviolet detection purchased from Merck. Anhydrous magnesium
(HPLC-UV), HPLC diode array detection (HPLC- sulfate and Sodium chloride were activated by
DAD) or HPLC mass spectrometry (HPLC-MS) heating at 250ºC for 4 h in the oven before use
are used for the determination of imidacloprid in and kept in desiccators. Pesticide technical
different environmental samples [7, 8]. HPLC-DAD formulations (Actara 25% WG), was supplied by
is a technique with more widespread use and suitable Syngenta Agro, Egypt and (Oshin 20% SG), was
for the separation and quantification of compounds supplied by Shoura Company, Egypt.
with high molar absorptivity, such as neonicotinoids [9].
Apparatus
Greenhouses production of crops requires Agilent 1100 HPLC equipped with diode array
pesticides applications due to high liability of detector (Agilent, Palo- Alto, CA USA) at UV
the crops to be infected with many pests, such wavelength 230 and 210 nm for thiamethoxam
as aphids, thrips and whiteflies, which cause and dinotefuran. An ODS C18 HPLC column (4.6
economic injury to pepper through direct injury, mm ´ 150 mm ´ 5μm) was used as the separation
virus transmission, leaf stunting, yellowing and column. Mobile phase consisted of acetonitrile
curling on mature plants. and water (90:10) and (60: 40) for thiamethoxam
and dinotefuran, respectively with a flow rate of
The objective of the present work was to 0.8 ml/min. The retention time of thiamethoxam
determine the dissipation behavior and the and dinotefuran under these conditions was 2.34
residues of dinotefuran and thiamethoxam in and 1.98 min, respectively.
pepper fruits under greenhouse conditions.

Egypt. J. Chem. 61, No. 2 (2018)

 DETERMINATION OF DINOTEFURAN AND THIAMETHOXAM RESIDUES ... 251

Standard preparation range within which detector response is directly

Stock solutions of thiamethoxam and proportional to the concentration of analyte in
dinotefuran were prepared by dissolving 10 mg samples. Standard solutions in terms of micro-
of the analytes (of accurate weight) in 100 ml liters, at variable concentrations, were divided
ethyl acetate and methanol, respectively to obtain into individual amounts, with the interval
solution concentration of 0.1 mg/ml. Working 0.01, 0.1, 0.5, 1, 2, 5 and 10 mg/kg for injected
standard solutions of 10, 5, 2, 1, 0.5, 0.1 and 0.01 solutions. The tests were repeated for three
μg/ml of each were prepared by appropriately times at each concentration, proving favorable
diluting the stock solutions with methanol. Stock linear relationship of the pesticides. Correlation
solutions were stored at -20 ± 2 oC, and working coefficients were 0.99 for dinotefuran and
standard solutions were stored in the dark £ 4 oC thiamethoxam.
when not in use. Matrix-matched calibration (MMC) was
Field experiment used to compensate for the matrix effects. The
Field experiment was carried out in experimental matrix effects were defined as the influence of
farm of Faculty of Agric. Cairo Univ. during 2016 one or more co-extracted components from the
season. Pepper plants were sprayed by dinotefuran sample on the measurement of thiamethoxam and
(Actara 20% SG) at 125 g/100-liter water and dinotefuran concentration. The presence of these
thiamethoxam (Oshin 25% WG) at the recommended effects is demonstrated by comparing the response
rate 20 g/100-liter water to determine the residues of produced from the thiamethoxam and dinotefuran
these chemicals in pepper fruits. Random samples in a pure solvent solution with the samples were
of the fruits were collected from the treated plants 0, first extracted and then spiked with thiamethoxam
1, 3, 5, 7, 10, 15 and 21 days’ post application for and dinotefuran in the same solvent at the same
dinotefuran and thiamethoxam. concentration levels (10, 5, 2, 1, 0.5, 0.1 and 0.01
mg/kg).
Sampling and storage:
Sampling was performed by randomly Matrix effects (%ME) were calculated using
collecting 2 Kg of pepper from each untreated and the equation:
treated areas (thiamethoxam and dinotefuran).
The collected samples were representative of all
plants in the area. First clean samples of pepper where
were collected from the control area, and then ME: the matrix effect
treatment of plants started on the previously M matrix: Slope of calibration curve in matrix.
mentioned dates, and sampling took place 2 h M solvent: Slope of calibration curve in the pure
after application of the initial deposits, repeated 1, solvent.
3, 5, 7, 10, 15 and 21 days afterwards to study the LOD means the validated lowest residue
dissipation of the pesticides. Field samples were concentration which can be quantified by routine
transported in iceboxes to the laboratory. monitoring with validated control methods defined
Extraction and clean up. as a signal-to-noise ratio (S/N) of 3:1. LOQ is the
The samples were extracted with modified lowest concentration of the analyte that has been
QuEChERS method [10], 10 g of weighed validated with acceptable trueness (70-120%) and
chopped sample (blank or spiked) was shaken precision (RSD ≤ 20%) by applying the complete
with 10 ml of acetonitrile in a 50-ml centrifuge analytical method defined as a signal-to-noise
tube then 4.00 g of anhydrous magnesium sulfate ratio (S/N) of 10:1. According to Dg-sanco, 2013
was added, and shaken for 1 minute. The tube was [11], the Limit of quantification should be ≤ MRL.
vortexed and centrifuged for 5 minutes at 4000 The trueness was determined from the
rpm. 6 mL of acetonitrile layer was transferred recovery assay results of samples spiked with
into a Polipropilene-single centrifuge tube which all the analytes at the levels (0.01-1 mg/kg), five
contains 150 mg PSA and 900 mg magnesium replicates per level used to check the recovery at
sulfate anhydrous. The sample was mixed acceptable mean recoveries are those within the
vigorously by vortexing for 1 min and centrifuge range of 70-120%.
extracted for 2 minutes at 6000 rpm.
Trueness was calculated using the following
Method validation
The linearity of a method is a measure of
Egypt. J. Chem. 61, No. 2 (2018)
 252 M. M. RABEA et al.

equation: coefficient (R2 = 0.99).

% R = (X/µ) × 100
The pesticide residue analysis study, the
%R: recovery percentage injected sample contained large amounts of the
X: experimental concentration of dinotefuran or unavoidably present co-extractives which are
thiamethoxam mg/kg responsible for the matrix effects occurring on
µ: calculated concentration of dinotefuran or the injector. The matrix effect was investigated by
comparing the slopes of calibration curves at (10,
thiamethoxam mg/kg
5, 2, 1, 0.5, 0.1 and 0.01 mg/kg) of dinotefuran and
The precision is a measure of how close results thiamethoxam in pepper and in pure solvent. The
are to another one (Repeatability (r)) was defined as % ME could be negative or positive and would
be classified in three categories: no matrix effect
standard deviation of measurement of dinotefuran
(between -20% and 20%), medium matrix effect
or thiamethoxam obtained using the same method (between -50% and -20%) and strong matrix
on the same samples in a single laboratory over a effect (below -50% or above 50%) [15, 16]. The
short period of time, during which differences in results showed that the matrix effect was -17.75%
the materials and equipment used and analysts for dinotefuran and 4.36% for thiamethoxam
involved will not occur. The value of ≤ 20% was which indicated that no interfering endogenous
used as the limit for RSD. Five replicates for each peak appeared and did not significantly suppress
recovery levels (0.01 – 1 mg/kg) per day on three or enhance the response of the instrument.
different days were used to check the precision.
The lowest validated level of dinotefuran
%RSD = (SD / M) × 100 and thiamethoxam with acceptable precision
where and trueness LOQ was 0.01 mg/kg for HPLC
analysis in pepper. According to Dg-sanco, 2013
SD: standard deviation of the replicates.
[11], the LOQ values are acceptable where LOQ
M: the mean value of the recovery. ≤. MRL (0.01 and 0.7 mg/kg for dinotefuran and
Statistical analysis thiamethoxam, respectively.
The dissipation kinetics of thiamethoxam and The trueness, bais or mean of recovery was
dinotefuran residues in pepper was determined by carried out in 5 replicates at 3 fortification levels
plotting residue concentration against elapsed time (1, 0.5, 0.01 mg/kg) by spiking 10 g of blank
after application and equations of best curve fit with samples with standard solution. The obtained mean
maximum coefficients of determination (R2) were recoveries range from 77-80% and 78-112% for
determined. For dissipation of thiamethoxam and dinotefuran and thiamethoxam, respectively with
dinotefuran in pepper, exponential relationships relative standard deviation (%RSD) ranged from
were found to be applicable corresponding to the 2.08 to 2.51 and from 1.92 to 2.14. According to
Dg-sanco, 2013 [11], the found mean recoveries
general first-order kinetics equation:
were in the acceptable range (70-120%). So, the
Ct=C0e-kt value showing that the method was sensitive and
suitable for the determination of dinotefuran and
where Ct represents the concentration of the thiamethoxam residue in pepper.
pesticide residue at the time of t, C0 represents
the initial deposits after application and k is the The repeatability precision (%RSD) involved
constant rate of pesticide dissipation per day. repeat of recovery levels (1, 0.5, 0. 01 mg/kg),
From this equation, the dissipation half-life five replicates for each level per day on three
periods (t1/2=ln 2/k), [12, 13, 14] of the studied different days. The (%RSD) value ranged from
insecticide were determined. 1.22 to 2.89 and 2.04 to 3.27 According to Dg-
sanco, 2013 [11], the obtained (%RSD) value was
Results within the acceptable range ≤20%.
Method Validation Dissipation of insecticide thiamethoxam and
The evaluations of calibration curve linearity dinotefuran in pepper.
of thiamethoxam and dinotefuran were done Thiamethoxam
based on injections of standard solutions prepared Dissipation of thiamethoxam in pepper fruits
in pure organic solvent methanol in series at (10, was studied during 21 days. The dissipation
5, 2, 1, 0.5, 0.1 and 0.01 mg/kg) for HPLC-DAD. pattern of thiamethoxam in pepper at different
Standard calibration curve of thiamethoxam and sampling intervals (0, 1, 3, 7, 10, 15 and 21 days)
dinotefuran was constructed by plotting analyte is presented in Table 1 and Fig. 2. The initial
concentrations against peak areas. The correlation deposit of thiamethoxam in pepper fruits was 1.38
Egypt. J. Chem. 61, No. 2 (2018)
 DETERMINATION OF DINOTEFURAN AND THIAMETHOXAM RESIDUES ... 253

mg/kg two hours after application. The residue of and 21 days of application, respectively. Based on
thiamethoxam in pepper fruits decreased to 1.27 the previous results, the calculated half-life period
mg/kg with 7.97% loss after 24 hours of application. (RL50) of thiamethoxam on pepper fruits was
The dissipation continued for thiamethoxam to 3.13 days. The maximum residue limit (MRL)
reach 0.72 mg/kg with 47.82% loss in the third of thiamethoxam in pepper fruits is 0.7 mg/Kg
day of application. The rapid dissipation was according to Codex Alimentarius Commission
found in the seventh day after spraying, which for Pesticide Residues (CAC/PR). 2009 [17]. The
thiamethoxam residue reached 0.083 mg/kg with results presented herein clearly show that pepper
93.98% loss. The degradation continued to reach fruits can be consumed safely by human after 4
0.061 mg/kg with 95.57% loss after 10 days after days from spraying with thiamethoxam.
application. The residues of thiamethoxam on
pepper decreased to 0.034 mg/kg with 97.31 % dinotefuran
loss and 0.01 mg/kg with 99.27% loss after 15 Data presented in Table 2 and Fig. 3

TABLE 1. Dissipation of thiamethoxam residue in pepper fruits.

Time after
Residues (mg/kg)±SD % loss % persistence
application
Initial 1.38±0.54 0.00 100
1day 1.27±2.87 7.97 92.03
3 days 0.72±1.05 47.82 52.18
5 days 0.39±2.59 71.73 28.27
7 days 0.083±2.01 93.98 6.02
10 days 0.061±0.54 95.57 4.43
15 days 0.034±0.81 97.31 2.69
21 days 0.01±0.24 99.27 0.73
RL50(days) 3.11
MRL 0.7
PHI (days) 4

Egypt. J. Chem. 61, No. 2 (2018)

 254 M. M. RABEA et al.

demonstrate the initial deposits as well as the and 0.01 mg/kg with 98.63 and 99.84% loss
residual behavior of dinotefuran in pepper fruits. after 7 and 10 days of application, respectively.
The initial deposit of dinotefuran in pepper fruits The residues became undetectable on 15th and
was 6.59 mg/kg two hours after application. The 21st day after application. Based on the previous
residue of dinotefuran in pepper fruits within results, the calculated half-life period (RL50)
the first 24 hours after application decreased to of dinotefuran in pepper fruits was 2 days. The
5.40 mg/kg with 18.06% loss. The amounts of maximum residue limit (MRL) of dinotefuran in
dinotefuran residue decreased to 1.28 mg/kg pepper fruits is 0.01 mg/Kg according to Codex
with high percent loss (80.58%) in the third day Alimentarius Commission for Pesticide Residues
of application. Data indicated that dissipation of (CAC/PR). 2009 [17], so the pepper fruits can be
dinotefuran residue was rapidly within the first consumed safely after 11 days of application.
three days after spraying. Residues of dinotefuran
in pepper fruits continued and reached to 0.09
TABLE 2. Dissipation of dinotefuran residue in pepper fruits.
Residues
Time after application % loss % persistence
(mg/kg)±SD
Initial 6.59±1.25 0.00 100
1day 5.40±0.95 18.06 81.94
3 days 1.28±1.01 80.58 19.42
5 days 0.67±1.38 89.83 10.17
7 days 0.09±2.09 98.63 1.37
10 days 0.01±0.22 99.84 0.15
15 days ND --- ---
21 days ND --- ---
RL50(days) 2
MRL 0.01
PHI 11

Egypt. J. Chem. 61, No. 2 (2018)

 DETERMINATION OF DINOTEFURAN AND THIAMETHOXAM RESIDUES ... 255

Discussion Conclusion
The evaluations of calibration curve linearity In this work, an HPLC-DAD analytical
of thiamethoxam and dinotefuran were done method based on QuEChERS sample pretreatment
with HPLC-DAD. The correlation coefficient procedures was used for the determination
(R2 = 0.99). The results showed that the matrix of dinotefuran and thiamethoxam residues in
effect was -17.75% for dinotefuran and 4.36% pepper fruits. The developed method is easy and
for thiamethoxam which indicated that no compatible for residue analyses of dinotefuran
interfering endogenous peak appeared and did not and thiamethoxam, the mean recoveries ranged
significantly suppress or enhance the response of from 77–80% and 78–112% respectively, and
the instrument. repeatability of the method, expressed as the
relative standard deviation, was lower than 3%.
The residual amount of thiamethoxam was The calculated half-life period (RL50) of tested
rapidly decreased during the third day of spraying pesticides on pepper fruits were 2 and 3.11 days
followed by gradually decreasing until the end of for dinotefuran and thiamethoxam, respectively.
experimental period, the lowest dissipation rate According to maximum residue limit (MRL) the
per day found from the seventh to tenth day of pre-harvest interval (PHI) of thiamethoxam and
application, while the highest value occurred in dinotefuran in pepper was 4 and 11 days after the
the first 24 hours of spraying. The pepper fruits treatment, respectively.
could be used safely for human consumption after
4 days from spraying with thiamethoxam, because Acknowledgements
the residues below the MRL of thiamethoxam on
pepper. Also, the initial deposit of thiamethoxam This work was supported by Faculty of
(Actara 25% WG) on pepper fruits was lower than Agriculture, Cairo University, Egypt.
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Journal of agricultural and food chemistry, 35(6),
859-864 (1987). DOI:10.1021/jf00078a003
Egypt. J. Chem. 61, No. 2 (2018)
 ‫‪DETERMINATION OF DINOTEFURAN AND THIAMETHOXAM RESIDUES ...‬‬ ‫‪257‬‬

‫تقدير متبقيات مبيدى داينوتيفيوران و ثياميثوكسام فى ثمار الفلفل بإستخدام طريقة‬

‫‪ QuEChERS‬وجهاز ‪HPLC/DAD‬‬
‫*‪1‬‬
‫منصور محمود ربيع‪ ، 1‬الدسوقى صبرى إبراهيم‪ ، 1‬داليا السيد الحفنى‪ 2‬و محمد عبدهللا بيومى‬
‫‪1‬قسم الحشرات األقتصادية والمبيدات – كلية الزراعة ‪ -‬جامعة القاهرة ‪ -‬مصر‬
‫‪2‬المعمل المركزى لمتبقيات المبيدات – القاهرة – مصر‬

‫تم تجميع عينات ثمار الفلفل عشوائيا من المناطق المعاملة بالجرعات الموصى بها لتحليل متبقيات المبيدات بها‬
‫بعد صفر ‪ 15 ، 10 ، 7 ، 5 ، 3 ، 1 ،‬و ‪ 21‬يوم من الرش بالتوازى مع عينات غير معاملة حيث تم تقدير‬
‫متبقيات مبيدى داينوتيفيوران و ثياميثوكسام فى ثمار الفلفل بإستخدام جهاز ‪ HPLC/DAD‬وكانت طريقة‬
‫اإلستخالص المتبعة هى ما يسمى بطريقة ‪ QuEChERS‬حيث تعتبر طريقة سهلة وسريعة وفعالة ورخيصة فى‬
‫تقدير متبقيات المبيدات وكانت معدالت اإلسترجاع للمركبين بهذه الطريقة تتراوح مابين ‪ %80-77‬و ‪%112-78‬‬
‫لكال من داينوتيفيوران و ثياميثوكسام على الترتيب‪ .‬وكانت حدود التقدير لهذه الطريقة ‪ 1 – 0.01‬ملجم‪/‬كجم لكال‬
‫المبيدين فى عينات الفلفل‪ .‬كانت الكمية األولية لمبيدى داينوتيفيوران و ثياميثوكسام فى ثمار الفلفل ‪1.38 ، 6.59‬‬
‫ملجم‪/‬كجم على الترتيب ‪ ،‬وأوضحت الدراسة أن فترة نصف العمر للمبيد داينوتيفيوران هى ‪ 2‬يوم فى حين بلغت‬
‫‪ 3.11‬يوم لمبيد ثياميثوكسام وذلك بناء على قيمة (‪ )MRL‬الخاصة بكال المبيدين والتى تقدر بـ ‪ 0.01‬و ‪0.7‬‬
‫ملجم‪/‬كجم على الترتيب ‪ ،‬وكانت قيمة (‪ 11 )PHI‬و ‪ 4‬يوم لكال من داينوتيفيوران و ثياميثوكسام على الترتيب‪.‬‬

‫)‪Egypt. J. Chem. 61, No. 2 (2018‬‬

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