Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
Research Article, Issue 1
Analytical Methods in Environmental Chemis try Journal
Journal home page: www.amecj.com/ir
AMECJ
Determination and analysis of pes ticide residues in eld-
grown and greenhouse-grown tomatoes using liquid
chromatography-mass spectrometry
Fatemeh Norouzi a,b, Maryam Faraji a,b,*, Ramezan Sadeghi c, Ali Faghihi-Zarandi d,
and Farshid Shabani Boroujeni e
a Environmental Health Engineering Research Center, Kerman University of Medical Sciences, Kerman, Iran
b Department of Environmental Health Engineering, Faculty of Public Health,
Kerman University of Medical Sciences, Kerman, Iran
c Department of Environmental Health of Engineering, Faculty of Health,
Shahrekord University of Medical Sciences, Shahrekord, Iran
d Department of Occupational Health Engineering and Safety at Work, Faculty of Public Health,
Kerman University of Medical Sciences, Kerman, Iran
e Department of Plant Protection, Faculty of Agriculture, University of Tabriz, Tabriz, Iran
ABSTRACT
The present s tudy aimed to extract pes ticide residues in the eld and
greenhouse-grown tomatoes and homemade pas te based on the quick,
easy, cheap, eective, rugged, and safe sample preparation method
(QuEChERS) before determined by the liquid chromatography-mass
spectrometry (LC-MS). The mean dierence in percentage reduction
of deltamethrin (DLM) and acetamiprid (ACT) in raw tomatoes of
greenhouse-grown was obtained at 91.42 and 90.00%, respectively,
which was insignicantly more than led condition (84.91% and
86.34%). Maximum reduction percentages of the DLM in pas te under
greenhouse and eld tomato conditions were achieved by more than
95.86% and 93.11%, respectively. The residual concentration of both
DLM (91.42%) and ACT (90.00%) in the greenhouse decreased more
than the eld (84.91% and 86.34%), respectively. Abamectin(ABA)
reached below the MRL in a shorter time after spraying (2 days).
Considering the pre-harves t interval (PHI) period of deltamethrin
and abamectin can reach their residual concentration to the MRL in
both conditions, which were determined by LC-MS. According to
the results of the current s tudy, 7 and 5 days can be sugges ted as
the PHI period of the acetamiprid for eld and greenhouse-grown
tomatoes, respectively. Therefore, using pes ticides in the proper
dosage, considering appropriate PHI, and harves ting can reduce their
residues in agricultural products.
Keywords:
Liquid chromatography-mass
spectrometry,
Analysis,
QuEChERS method,
Pes ticide residues,
Field and Greenhouse-grown tomatoes
ARTICLE INFO:
Received 14 Nov 2022
Revised form 20 Jan 2023
Accepted 12 Feb 2023
Available online 29 Mar 2023
*Corresponding Author: Maryam Faraji
Email: m.faraji@kmu.ac.ir and m_faraji28@yahoo.com
https://doi.org/10.24200/amecj.v6.i01.234
------------------------
1. Introduction
Tomato, scientically known as Solanum
Lycopersicum, is one of the world’s mos t widely
used and popular vegetables. It’s used as raw and
processed due to having high antioxidants such
as ascorbic acid, vitamins E and A, carotenoids,
avonoids, and phenolic acid that can reduce the risk
of cardiovascular diseases and prevent diabetes and
cancer [1, 2]. Several pes ticides are used to maintain
agricultural products. Improper consumption of
pes ticides in farm products and non-compliance
with the pre-harves t interval (PHI) period can
101
cause adverse eects due to the presence of residual
pes ticides in the crops [3]. Therefore, the European
Union (EU) has set a maximum pes ticide residue
limit (MRL). The MRLs for s tudied pes ticides in the
present s tudy included acetamiprid, deltamethrin,
and abamectin in tomatoes are dened as 500,
70, and 90, respectively, regardless of the growth
conditions [4, 5]. Ratnamma et al.’s s tudy on the
residual acetamiprid in okra showed that using 10 g
and 20 g of 20% acetamiprid per hectare led to the
residual of 2.034 and 4.044 mg kg-1, respectively
[6]. The results of Yazdan Pak et al.’s s tudy on
the residual pes ticides in the greenhouse tomatoes
during 2, 5, 7, 10, 14, 17, and 21 days after spraying
showed that the residual of acetamiprid, diazinon,
imidacloprid, and pirimicarb declined after the PHI
period approached [7]. Mohamed et al. reported that
imidacloprid decomposed fas ter than acetamiprid
in tomatoes grown under greenhouse conditions
[8]. Iran ranks seventh globally, accounting for
4.7% of the total world production of tomatoes,
with an annual production of 5.8 million tons
and an average yield of 38 tons per hectare [9].
According to the high production and consumption
of raw and processed tomatoes in Iran and the use
of high levels of pes ticides in their cultivation, this
s tudy aimed to determine deltamethrin, abamectin,
and acetamiprid residues in cultivated tomatoes
in the eld and greenhouse as raw and home
processed using QuEChERS (quick, easy, cheap,
eective, rugged, and safe) method and analysis of
residual pes ticides by liquid chromatography-mass
spectrometry (LC-MS) method.
In this s tudy, the residual concentrations of
pes ticides, including acetamiprid, deltamethrin,
and abamectin, were extracted and determined by
the QuEChERS procedure coupled to LC-MS. The
residual concentration of three high-consumption
pes ticides of Iran in raw and processed tomatoes
was determined and compared. Also, the residual
concentration of the three mentioned pes ticides
in outdoor-grown (eld-grown) and greenhouse
tomatoes were s tudied and compared together.
The current s tudy was innovative in comparing the
residual pes ticides.
2. Material and Methods
This s tudy was done in several s tages included
planting and spraying of tomatoes in eld and
greenhouse and harves ting, preparation of the
samples through the QuEChERS method and their
analysis of samples via LC-MS and s tatis tical
analysis of the data. S tudy s tages are illus trated in
Schema 1.
Schema 1. S tudy s tages of sampling, the QuEChERS preparation method and determination by LC-MS
Determination and analysis of pes ticides by LC-MS Fatemeh Norouzi et al
102
2.1. Ins trumental
LC-MS is an accurate and precise method to
separate, identication and analysis of compounds.
It can be successfully and eciently adopted for
quality control analysis of compounds. It can
also be used in combination with other analytical
methods to further elucidate the components of
mixtures [17]. LC-MS (model: Waters Alliance
2695 (UK)) using a matrix-matched method was
used to analyze samples in the present s tudy. The
type of detector was Micromass Quattro Micro
API Triple Quadruple Mass Spectrometer (UK).
Column specications were Waters Sunre C18
Column 100 Å, 150 mm × 2.1 mm × 1.5 µm. The
samples of 20 µL were injected into the device.
Chromatograms of the s tandard samples to provide
calibration curve have been illus trated in Schema 2.
2.2. Chemicals and reagents
S tandards of Acetamiprid (99.9%), abamectin
(95%), deltamethrin (98.5%), deltamethrin
(2.5%EC), acetamiprid (20%SP), abamectin
(1.8%EC) and other chemicals and reagents included
acetonitrile, anhydrous magnesium sulfate, the
internal s tandard of triphenyl phosphate, sodium
chloride, trisodium citrate dihydrate, disodium
hydrogen citrate, primary, secondary amine (PSA),
and carbon adsorbent (C18) were purchased from
Sigma Aldrich, Germany. Dilutions of 50, 100,
250, 500, and 1000 ng g-1 were used to plot the
calibration curve of the pes ticides using a matrix-
matched method. The limit of detection (LOD),
the limit of quantication (LOQ), the regression
equation of calibration, and the MRL for the s tudied
pes ticides are mentioned in Table 1.
2.3. Planting and spraying of tomatoes in the
eld and greenhouse
A eld and a greenhouse were respectively
considered for planting tomatoes outdoors and in
a greenhouse in the summer of 2020. The average
temperature in the s tudy period, namely the summer
and fall of 2020, in the greenhouse and eld was
20±3 and 8.9 °C. Four terraces were allocated for
each treatment in the greenhouse and the eld. The
dis tance between tomato plants was considered
to be 40 cm. Dis tances of 120 and 100 cm were
dened between terraces in the greenhouse and
eld, respectively. An empty terrace was spaced
between the terraces to eliminate the eects of
overlap and possibly dispersion of pes ticides
through the wind. The control samples were grown
on the unsprayed terrace. Randomized spraying
was performed with a 20 L calibrated rechargeable
back sprayer (model: IAC CODE: E2) according to
the doses recommended by the Iran Plant Protection
Organization, including 0.6 liters per hectare for
abamectin, 300 cc per hectare for deltamethrin, and
Schema 2. Chromatograms of the ve s tandard pes ticides, including acetamiprid, deltamethrin,
and abamectin for calibration curve
Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
103
0.5 kg per 1000 liters of water for acetamiprid. The
physical and chemical characteris tics of the s tudied
pes ticides [10-12] are reported in Table 2.
2.4. Sample harves ting
According to the manufacturer’s ins trument, the
PHI period for deltamethrin and abamectin was
dened as three days. Therefore, sample harves ting
in the case of deltamethrin and abamectin was
done in the sugges ted PHI period and before and
after that, 1, 2, 3, 4, and 5 days after spraying. The
manufacturer did not dene the PHI period for
acetamiprid. Thus, sample harves ting in the case of
acetamiprid was done according to similar s tudies
[13, 14], and the farmers’ performance was 3, 5, 7,
9, and 11 days after spraying. After time elapsed, 2
kg samples harves ted from dierent terraces were
mixed and, after coding, placed in a black bag and
maintained at 4 °C. Then, part of the samples was
homogenized after washing to measure the residual
pes ticide in the raw sample, and the other part was
used to prepare homemade tomato pas te. To make
tomato pas te, the washed tomatoes were chopped,
salted, and s tored at room temperature for 24 hours.
Then, the tomato juice was s trained and heated at
96 °C for one hour. After cooling, the samples were
packaged and coded separately.
Also, one sample of each treatment was taken
one hour after spraying to compare the amount of
pes ticide residues in washed and unwashed tomatoes.
Then, the samples were divided into two equal parts;
one part was washed with tap water, and another part
was reserved unwashed. Finally, the samples were
maintained at -21 °C until experiments.
Table 1. Limit of detection (LOD), the limit of quantication (LOQ), the regression equation, and the maximum
residue limit (MRL) for the s tudied pes ticides
Pes ticide Abamectin Deltamethrin Acetamiprid
Chemical s tructure
Chemical formula C95H142O28 C22H19Br2NO3C10H11ClN4
MW (g mol-1)1732.1 505.21 222.68
Water solubility 1.21 mg L-1 at 25 ºC <0.002 mg L-1 at 25 ºC 4.25 g L-1 at 25 ºC
Octanol/water partition
coecient 4.4 6.10 0.8
Chemical Family
Insecticide, a natural
fermentation product
of soil-dwelling
actinomycete,
S treptomyces avermitilis
Pyrethroid insecticide Neonicotinoid insecticide
Table 2. Physical and chemical characteris tics of the s tudied pes ticides
Pes ticide LOD
(mg kg-1)
LOQ
(mg kg-1)
Regression equation
of calibration R2*MRL
Abamectin 13.2 40 y=3.37761x +0.313794 0.9848 0.09
Deltamethrin 13.2 40 y=7.78742x-7.7343 0.9931 0.07
Acetamiprid 13.2 40 y=11.8763x-8.70884 0.9946 0.50
*MRL: maximum residue limit of the European Union
Determination and analysis of pes ticides by LC-MS Fatemeh Norouzi et al
104
2.5. Preparation and analysis of samples
The QuEChERS method, with its high sensitivity, is
used to extract the residual pes ticides in the products
in many reference laboratories [15]. To extract
pes ticides in the current s tudy by the QuEChERS
method, each sample was homogenized in a blender,
and 10 g of samples were transferred to the centrifuge
tube. Then, 10 mL of acetonitrile and 100 µL of the
internal s tandard of triphenyl phosphate were added
to each centrifuge tube at the concentration of 10
ppm. Next, 4g anhydrous magnesium sulfate, 1.0 g
sodium chloride, 1.0 g Trisodium citrate dehydrate,
and 0.5 g disodium hydrogen citrate were added to
each centrifuge tube after a vigorous shake for one
minute. Again, the mixture was vortexed for one
minute at 5000 rpm for 5 minutes at -10 °C. Then, 3
mL of the transparent top layer was transferred into
the tube containing 75 mg PSA, 450 mg anhydrous
magnesium sulfate, and 75 mg C18 adsorbent.
Samples were nally moved into a vial after vortex
for one minute and re-centrifuged [16]. Residual
concentrations of pes ticides in the samples were
measured by the method of LC-MS. LC is an accurate
and precise method to separate, identify and analyze
compounds. It can be successfully and eciently
adopted for quality control analysis of compounds. It
can also be combined with other analytical methods
to further elucidate the components of mixtures [17].
2.6. S tatis tical analysis
S tatis tical analysis was performed using R software
version 3.4.1. Results were reported as the mean
± s tandard deviation. The mean concentration of
pes ticides in dierent samples was compared via
ANOVA. P-value < 0.05 was considered as the
signicance level.
3. Results and discussion
3.1. Deltamethrin
The EU has determined the deltamethrin
MRL in tomatoes as 70 µg kg-1. The residual
concentration of deltamethrin was reached less
than MRL in the eld and greenhouse on the
fth and fourth days after spraying, respectively
(Fig. 1a). Therefore, considering the PHI period
for deltamethrin, which has dened to be three
days according to the manufacturer’s ins trument,
its residual concentration met the MRL in both
conditions. Residual concentration and reduction
percentage of deltamethrin in raw tomato and
pas te of eld- and greenhouse-grown are shown
in Table 3. Comparison between the mean residual
concentration of deltamethrin at dierent harves t
times from 1 to 5 days with the MRL showed a
non-signicant dierence in the eld (p = 0.14)
and greenhouse (p = 0.43). The mean dierence
of percentage reduction in raw tomato between
the eld (84.91%) and greenhouse (91.42%)
conditions was not signicant (p=0.18). The
residual concentration of deltamethrin in tomato
pas te made from both eld-grown and greenhouse-
grown products showed a decreasing trend (Fig.1b).
The concentration of deltamethrin in the pas te from
eld products was decreased up to 95% on the fth
day after spraying. While its removal was more
than 95% in the greenhouse products (Table 3).
3.2. Abamectin
The comparison of the residual concentration
of abamectin in the eld and greenhouse-grown
tomatoes with the MRL of 90 µg kg-1 was shown in
Figure 2a. The residual concentration of abamectin
was less than MRL on the second day after spraying
in both growing conditions (58 µg kg-1 and 77 µg
kg-1, respectively). The PHI period for abamectin
has been dened to be three days based on the
manufacturer’s ins trument. Thus, considering the
PHI period for abamectin can reach its residual
concentration below the MRL in tomatoes grown
in the eld and greenhouse. The decreasing trend
was observed in the residual concentration of
abamectin in the tomato pas te made from eld-
grown and greenhouse-grown products (Fig. 2b).
The concentration of abamectin was reduced to
more than 89% in the pas te made from crops in both
conditions after ve days (Table 3). The residual
concentration of abamectin in the pas te can reach
below 40 µg kg-1 in the eld and 46 µg kg-1 in the
greenhouse, considering the PHI period in tomato
(three days).
Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
105
Fig. 1. The comparison of the mean residual concentrations of deltamethrin in eld-grown
and greenhouse-grown tomatoes (a) and pas te (b)
Determination and analysis of pes ticides by LC-MS Fatemeh Norouzi et al
106
Fig. 2. The comparison of the mean residual concentrations of abamectin in eld-grown
and greenhouse-grown tomatoes (a) and pas te (b) and the EU maximum residue limits
Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
107
Table 3. Residual concentration and reduction percentage of deltamethrin, abamectin, and acetamiprid
in raw tomato and pas te of eld-grown and greenhouse-grown
Tomato pas teRaw tomatoes
Pes ticide
GreenhouseFieldGreenhouseField
PR
(%)
RC
(µg kg-1)
PR
(%)
RC
(µg kg-1)
PR
(%)
RC
(µg kg-1)
PR
(%)
RC
(µg kg-1)
Day
91.3683.5079.45198.7086.36131.9169.74292.621
Deltamethrin
93.5762.1088.91107.2089.9397.3081.92174.802
95.0847.9092.7769.9192.5171.6188.27113.403
>95.86<4094.5752.5093.8059.8291.5381.914
>95.86<4095.6941.6094.5052.5293.1166.605
-
-90.2893.9891.4282.6384.91145.87
Mean
-
----70-70
MRL
-
----0.43*0.18**0.14*
p-value
73.21101.6079.0679.4070.38112.3475.5892.601
Abamectin
81.7769.1187.4747.5079.7476.8084.7557.802
87.8446.12>89.45<4085.8953.5088.1844.813
>89.45<40>89.45<4088.2144.70>89.45<404
>89.45<40>89.45<40>89.45<40>89.45<405
--------
Mean
-------90
MRL
--------
p-value
91.27328.1187.32476.3385.67538.4177.76835.613
93.53242.9190.93340.7188.85418.9184.63577.6225
94.25215.8192.61277.4090.42359.7187.69462.337
Acetamipride
94.85193.2193.77234.1191.97301.6290.11371.619
95.41172.5194.39210.6193.08259.8191.49319.5211
93.86230.5191.80307.8390.00375.6986.34513.34
Mean
-----500-500
MRL
--0.19**--0.06*0.22**0.89*
p-value
*Comparison between mean concentration and maximum residue limit (MRL),
**Comparison between percentage reduction in eld and greenhouse
RC: Residual concentration
PR: Percentage reduction
Determination and analysis of pes ticides by LC-MS Fatemeh Norouzi et al
108
3.3. Acetamiprid
The EU dened the concentration of 500 µg kg-1 as
the MRL level for acetamiprid. The mean residual
concentration of acetamiprid in the eld, greenhouse,
and MRL level is compared in Figure 3a. The results
showed that the residual concentration of acetamiprid
in raw tomato in the eld from the seventh day (462
µg kg-1) and in the greenhouse from the fth day
(419 µg kg-1) reached below the MRL by LC-MS.
The manufacturer has not dened the PHI period for
acetamiprid. Therefore, the acetamiprid PHI period
of 7 days for the eld-grown and 5 days for the
greenhouse-grown tomato can be sugges ted based
on the results of the current s tudy. The dierence
in the mean reduction percentage of acetamiprid in
the eld-grown (86.34%) and greenhouse-grown
(90.00%) samples were not signicant (p=0.22).
Comparing the mean residual concentration of
acetamiprid in raw tomato and the MRL (500 µg
kg-1) showed a non-signicant dierence in the eld
(p=0.89) and greenhouse (p=0.06). The residual
concentration of the acetamiprid in the tomato pas te
after spraying eld-grown and greenhouse-grown
products followed a decreasing trend (Fig. 3b). The
concentration of acetamiprid was approximately
reduced to 95% in the pas te made from crops in
both conditions after 11 days (Table 3). The mean
percentage reduction of acetamiprid in the pas te
from greenhouse crops (93.86%) was insignicantly
(p = 0.19) more than eld crops (91.80%).
Elbashir et al. measured the residual concentrations
of fenpropathrin, λ-cyhalothrin, and deltamethrin in
eld-grown tomatoes for 30 days. The results showed
that the pes ticide residues of fenpropathrin after 27
days, λ-cyhalothrin after 18 days, and deltamethrin
after three days immediately after washing reached
below the MRL dened by the Codex and the EU [18].
In Salghi’s s tudy on evaluating residual pes ticides’
organochlorine, pyrothyroid, and dicarboximide
in greenhouse-grown tomatoes, the residual
concentration of deltamethrin was reported in the
range of 1-0.01 mg kg-1. The residual concentration of
pes ticides in the two s tudied samples was higher than
the MRL [19]. Due to the Raei’s s tudy, the results
of deltamethrin in greenhouse-grown cucumber
showed that the residual concentration of pes ticide
reached the allowable limit (0.2 mg kg-1) on the fth
day after spraying and was not measurable on the
seventh day after it [20]. In Abdelfatah’s s tudy on the
residual concentrations of abamectin, acetamiprid,
spinosad, diniconazole, penconazole, and pronil in
the eld-grown tomatoes, residual concentrations of
abamectin and acetamiprid were reported one hour
after spraying as 5.80 and 1.10 mg kg-1, respectively.
The results of this s tudy showed that ten days after
spraying with abamectin and one day after spraying
with acetamiprid, the residual pes ticides reached
below the EU MRL [21]. The s tudy of Fujita et al
on the residual amount of acetamiprid, azoxys trobin,
permethrin, and dinotefuran in eld-grown and
greenhouse-grown lettuce showed that the residual
concentrations of pes ticides in the greenhouse crop
were approximately the same as in the eld, but for
dinotefuran, the residual pes ticides in the greenhouse
crop were higher than that in the eld [22]. According
to Badawy et al.’s s tudy, the residual concentrations of
acetamiprid and imidacloprid in greenhouse-grown
tomatoes reached below the Europe MRL within
three days and ve days after spraying, respectively
[8]. The results of Chen et al.’s s tudy on the residual
concentration of propamocarb in greenhouse-grown
and eld-grown vegetables showed that the residual
of propamocarb in the greenhouse crop was higher
than the eld crop [23].
3.4. Comparison of dierent condition
In comparison between mean reduction percentages
of pes ticides in tomato grown in dierent condition
in the present s tudy, it can be s tated that residual
concentration of both deltametrin (91.42%) and
acetamiprid (90.00%) in the greenhouse was
decreased more than eld (84.91 and 86.34%,
respectively) by LC-MS. Abamectin reached below
the MRL in a shorter time after spraying (2 days)
compared to other pes ticides. The extent of pes ticide
residues in the agricultural products depends on
several factors such as the properties of pes ticide,
its formulation and applied concentration, light,
temperature, plant morphology and plant growth
factors [24].
Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
109
Fig. 3. The comparison of the mean residual concentrations of acetamiprid in eld-grown
and greenhouse-grown tomatoes (a) and pas te (b)
Determination and analysis of pes ticides by LC-MS Fatemeh Norouzi et al
110
In comparison between raw tomato and tomato pas te
in both grow condition, it was found that processing
of the raw tomato through cooking could decrease
the concentration of pes ticides in all experiments
by LC-MS. Dierence of residual concentration of
pes ticides in the raw and processed products was
found to be in the range of 0-10%, and a signicant
reduction was not observed with the processing
product. In Medina et al.’s s tudy evaluating the eect
of cooking on the residual pes ticides deltamethrin,
penconazole, cresoxime methyl, cyproconazole,
epoxiconazole, and azoxys trobin in rice, the results
reported the reduction of pes ticides as 20.73% to
57.72% for home cooking, 32.74% to 70.39% for
washing with excess water, and 68.87% to 87.50% for
soaking rice before cooking, respectively [25]. The
results of Romeh’s s tudy examining the processing
process on the residual acetamiprid in eld-grown
eggplant showed that washing 24.73%, boiling
56%, grilling 99%, and frying 46.24% aected the
reduction of its residual one day after spraying with
the recommended dose [26]. In 2016, Hana et al.
examined the reduction of non-sys temic and low-
sys temic (indoxacarb, chlorfenapyr, and fenarimol)
and sys temic (acetamiprid) pes ticides in okra after
the cooking process. The residual acetamiprid was
reduced up to 90% using cooking methods, indicating
that the tissues of the okra disintegrated during
cooking, so the internal remnants of acetamiprid
were exposed to water dissolution and thermal
decomposition [27]. The reduction percentage of
pes ticides in washed and unwashed tomato samples
was compared. The signicant eect of reducing the
residual pes ticides of abamectin, deltamethrin, and
acetamiprid was observed after washing with tap
water. Rinsing with tap water reduced the residual
concentrations of acetamiprid, abamectin, and
deltamethrin in the crops harves ted during one hour
after spraying up to 66.85%, 51.62%, and 50.52%,
respectively (Table 4). Acetamiprid, as a sys temic
pes ticide, with the highes t solubility in water (4250
mg L-1), had the highes t reduction percentage after
washing compared to the other pes ticides. Washing
is the rs t s tep in the food preparation process and
processing methods. Many residual pes ticides can
be removed by washing them with tap water. Various
factors aect the residual pes ticides after washing,
including the location of the pes ticide in the crop
(on the surface or in the tissue), washing method,
soaking time, physicochemical properties of the plant
and pes ticide, and the type of pes ticide. Pes ticides
with high water solubility can be more easily
eliminated, probably due to their reduced tendency
to enter the inner layers [24, 28, 29]. Ajeep et al.’s
s tudy on the eect of washing with tap water and
washing with an acetic acid solution on the residual
amount of ve insecticides (dimethoate, carbaryl,
chlorpyrifos, cypermethrin, and fenvalerate) and
one herbicide (2, 4-dichloro phenoxy acetic acid) in
tomato showed that both washing methods reduced
the concentration of pes ticides by a maximum of
63.08% [30]. In Shalaby’s s tudy, it was reported that
washing with tap water and acetic acid (1%) could
decrease the residual concentrations of abamectin
and buprofezin in eggplant and pepper plants two
hours after spraying up to 21.86% for washing with
water and 41.68% with acetic acid [31]. In Hana et
al.’s s tudy on okra, the initial residual concentration
for chlorfenapyr and acetamiprid was reported to be
7.5 mg kg-1 and 0.8 mg kg-1, respectively, which after
washing the okra with water, the residual reduction
percentage was reported to be 90% for chlorfenapyr
and 48% for acetamiprid. This nding is contrary to
the water solubility of two s tudied pes ticides [27].
In Elbashir et al.’s s tudy, the residual concentrations
of fenpropathrin, λ-Si haloterine, and deltamethrin
in outdoor-grown tomatoes were measured over 30
days. The results showed that the residual pes ticides
fenpropathrin after 27 days, λ-Si haloterine, after 18
days, and deltamethrin after three days in unwashed
samples reached below the MRL set by the Codex
and the EU. This amount immediately after washing
reached below the MRL in the washed samples
[18]. Moreover, some methods such as ultrasound-
assis ted dispersive micro solid-phase extraction,
micro-column solid-phase extraction, adsorption
(silver nanoparticles, Sulde Nanoparticles) were
used for extraction process [33-38]. The results
of similar s tudies were compared with proposed
methods in Table 5.
Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
111
4. Conclusion
The present s tudy aimed to inves tigate the residual
concentrations of pes ticides deltamethrin, abamectin
and acetamiprid in eld-grown and greenhouse-
grown tomatoes as raw and processed in the form
of homemade tomato pas te by LC-MS. The rank
of reduction percentage of pes ticides at the end of
the harves t period in the raw and pas te products
under both conditions followed as deltamethrin,
acetamipride and abamectin. Considering the PHI
period for deltamethrin and abamectin (3 days) can
reach their residual concentration to the MRL in both
conditions. According to results of the current s tudy,
the times of 7 days and 5 days can be sugges ted as
PHI period of the acetamiprid for eld-grown and
greenhouse-grown tomato, respectively. According
to the data obtained from the current s tudy and
the reduction percentage of the residual amount of
Table 5. Comparison of proposed method based on LC-MS technique with the published similar s tudies
Pes ticide Ins trument Product Condition Pes ticide Residues Ref.
Acetamiprid HPLC Tomato Greenhouse
Acetamiprid residues were below the already
es tablished European maximum residue
limits (EU MRLs) (0.5 mg/kg) 3 days after
application.
[8]
Abamectin HPLC Tomato Field
The maximum residues level (MRL) values
set by EU for abamectin are 0.02 mg/kg (EU,
2005). Based on these MRL values, PHIs
were 7 d.
[21]
Acetamiprid HPLC Tomato Greenhouse
The residual amount of acetamiprid
pes ticides in tomatoes is decreasing as the
PHI approaches.
[32]
Acetamiprid LC-MS/MS Lettuce Field and
Greenhouse
No clear dierence between the two growing
conditions was observed. [22]
Acetamiprid
LC-MS Tomato Field and
Greenhouse
The reduction rate of acetamiprid residue in
tomato was fas ter in greenhouse conditions
than in the eld.
Deltamethrin
The reduction rate of delthamethrin residue
in tomato was fas ter in greenhouse conditions
than in the eld.
This
Work
Abamectin
The reduction rate of abamectin residue in
tomato was fas ter in the eld than in the
greenhouse.
Table 4. Comparison of reduction percentage of deltamethrin, abamectin, and acetamiprid in unwashed
and washed tomato
Pes ticide Unwashed Washed Reduction (%)
Acetamiprid 3758.40 1245.80 66.85
Abamectin 967.10 467.80 51.62
Deltamethrin 379.20 187.60 50.52
Determination and analysis of pes ticides by LC-MS Fatemeh Norouzi et al
112
pes ticide from raw product to processed product
under eld and greenhouse conditions, it was found
that the dierence was in the range of 0-10% and
signicant reduction was not observed with the
processing product. The general conclusion that can
be inferred from this s tudy was that the highes t and
mos t remarkable reduction in the residual amounts
of pes ticide was related to the washing s tep, which
can reduce the residual pes ticide up to 66% which
analyzed by LC-MS. It can be sugges ted to s tudy
the initial residues in unwashed, washed, and
processed samples, and the residual concentration of
pes ticides in the soil during the harves t period, and
environmental eects in future s tudies.
5. Acknowledgment
The authors would like to acknowledge the Vice-
Chancellor for Research and Technology of Kerman
University of Medical Sciences for nancial
supports. The datasets analyzed during the current
s tudy are available from the corresponding author on
reasonable reques t. FN performed executive part of
the s tudy; RS performed the ins trumental analysis;
FSB analyzed data, and MF designed and managed
the s tudy.
6. Funding
This work was extracted from the Mas ter of Science
thesis supported by the Vice-Chancellor for Research
and Technology of Kerman University of Medical
Sciences under grant number 99000482.
7. Conicts of interes t
The authors declare that they have no known
competing nancial interes ts or personal relationships
that could have appeared to inuence the work
reported in this paper. This work was supported by
the Vice-Chancellor for Research and Technology
of Kerman University of Medical Sciences under
the code of research ethics certicate IR.KMU.
REC.1399.600.
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Anal. Methods Environ. Chem. J. 6 (1) (2023) 100-114
