Food Control xxx (xxxx) xxx

Contents lists available at ScienceDirect

Food Control
journal homepage: www.elsevier.com/locate/foodcont

Pesticides residues on Loquat: A minor crop in Lebanon

Mohamad I. Abou Zeid a, Mireille Kallassy Awad a, Khalil C. Melki b, Yusuf Abou Jawdah c, Adla
M. Jammoul d, *
a
Faculty of Science, Biotechnology Laboratory, UR EGP, Saint- Joseph University, B.P. 11-514, Riad El Solh, Beirut, 1107 2050, Lebanon
b
Unifert S.a.l., P.O. Box 11-6937, Riad El Solh, Beirut, 1107 2230, Lebanon
c
Department of Agriculture, Faculty of Agricultural & Food Sciences, American University of Beirut, Bliss Street, P.O. Box 11-0236, Riad El-Solh, 1107-2020, Beirut,
Lebanon
d
Lebanese Agricultural Research Institute, Food Department, Fanar P.O. Box: 2611, Lebanon

A R T I C L E I N F O A B S T R A C T

Keywords: Loquat in Lebanon is subjected to sprays by a variety of unregistered pesticides, as is the case with minor crops in
Loquat many parts of the world, to protect it from pests mainly scab. This malpractice would raise consumer’s health
Minor crops safety issues related to pesticides residues that could be avoided if the pesticides industry worldwide is not
Pesticide residues
reluctant in investing in the registration of minor crops pesticides. Penconazole is registered as a fungicide
Food safety
Penconazole
against scab on apples and pears in Lebanon without prior supervised field trials, but it is not registered on
Dissipation loquat.
PHI The aims of this study are to screen and quantify the range of pesticide residues in 128 loquat samples
gathered from Lebanese market between 2017 and 2019, study the dissipation behavior of penconazole on apple
and loquat in the field, confirm the critical good agricultural practices (cGAP) of penconazole on apples and
propose a pre-harvest interval (PHI) for penconazole on Loquat in Lebanon.
The samples were analyzed using a validated MRM method on apple with GC-MS/MS and LC-MS/MS deter­
mination. A total of 51 samples were irregular in terms of the pesticides residues found, with, residues of un­
authorized pesticides detected on 48 samples. The most frequently encountered unauthorized pesticides banned
in Lebanon were: cypermethrin (10.9%), dimethoate (6.25%), methomyl (6.25%), carbendazim (3.1%), and
thiametoxam (2.3%). Penconazole dissipated following a first order kinetic dissipation model on apple and
loquat. The half-life calculated on apple and loquat were 8.56 days and 9.49 days, respectively. A PHI = 14 days
can be proposed for loquat with a MRL of 0.07 mg/kg without any food safety issues raised with the same cGAP
practiced on apple.

1. Introduction minor crops and minor uses, the basic issue revolves around the avail­
ability of sufficient safe and effective pesticides registered for use on
Three global minor use summits (Global Minor Use portal, 2019), specialized crops (Baron et al., 2016). This unavailability is created by
IR4 project in Northern America (Baron, Holm, Kunkel, Schwartz, & the reluctance of the pesticides industry to invest in minor crops and
Markle, 2016), Specific Off Label Approval (SOLA) in UK (Hillocks, minor use registration, and to hold additional concomitant liability as an
2012), European Union MU data base (EUMUDA) and “coordinated IPM outcome of new registrations, with no justified revenue returns (Fen­
in Europe program” (Lamichhane et al., 2015) and many regulations are nimore & Doohan, 2008; Kunkel, 2012). Farmers, on the other hand,
all part of the worldwide effort to address the different facets of the challenged by pests threatening their produce (Fennimore & Doohan,
“minor crop problem”. “Minor uses are those uses of plant protection 2008), find themselves obliged to use unauthorized pesticides.
products (defined in relation to crops and pests) in which either the crop Loquat, Eriobotrya japonica Lind. is an evergreen of the Rosaceae
is considered to be of low economic importance at a national level family with 3 vegetative flushes a year and harvest during spring. It is a
(minor crop), or the pest is of limited importance on a major crop (minor subtropical tree, widespread in the Mediterranean region (Llácer, G.,
pest)” (EPPO, 2007). Although organizations differentiate between Badenes, M. L., & ), with only small areas of production, which makes

* Corresponding author.
E-mail address: [email protected] (A.M. Jammoul).

https://doi.org/10.1016/j.foodcont.2021.108297
Received 18 November 2020; Received in revised form 11 May 2021; Accepted 30 May 2021
Available online 10 June 2021
0956-7135/© 2021 Elsevier Ltd. All rights reserved.

Please cite this article as: Mohamad I. Abou Zeid, Food Control, https://doi.org/10.1016/j.foodcont.2021.108297
M.I. Abou Zeid et al. Food Control xxx (xxxx) xxx

the description of minor crop very suitable (EUROPEAN COMMISSION, representative of the commodity group that includes both apple and
2017). In Lebanon, it only occupies about 426.2 ha out of 230,000 ha of Loquat (EUROPEAN COMMISSION, 2017). Bearing in mind what Ripley
the total cultivated areas and is concentrated in South Lebanon in an et al. (Ripley, Ritcey, Harris, Denommé, & Lissemore, 2003) concluded
area of 348.3 ha, while the other 75 ha are spread all over Lebanon in their study that pesticide recommendations cannot always be
(Lebanese Ministry of Agriculture/FAO, 2017). Though it is considered a extended to specialty crops without an investigation of the changes in
minor crop, it has a certain economic importance as its produce is not preharvest intervals to prevent violations of the maximum residue
only consumed locally as a fruit delicacy but is also exported to regional limits.
markets, which have become increasingly demanding in terms of The aims of this study are to screen and quantify the range of pes­
compliance to pesticide residues safe limits. ticides residues in loquat samples from Lebanese market, study the
Loquat’s growing habit of flourishing in high humidity microcli­ dissipation behavior of penconazole on apple and loquat, confirm the
mates and soils makes it prone to a variety of pests, mainly the most cGAP of penconazole on apples and propose a pre-harvest interval (PHI)
detrimental apple scab Venturia inaequalis (González-Domínguez, for penconazole on loquat in Lebanon.
Armengol, & Rossi, 2017).
Due to the fact that difenoconazole is the only pesticide registered in 2. Materials and methods
Lebanon on loquat, Loquat has earned the title of being an orphan crop
in the sense that not enough pesticides are registered on it to control its 2.1. Chemicals and reagents
pests (Lebanese Ministry of Agriculture, 2019). To avoid huge economic
losses of their crop, Lebanese growers spray all kinds of fungicides and The reagents used were of analytical grade. The pesticide standards
insecticides known to chemically control scab and fruit flies, regardless of high purity grades (>99%) were purchased from Dr. Ehrenstorfer
of whether or not these pesticides are authorized for use on Loquat. (Augsburg, Germany). Individual stock solutions were prepared at 1000
Similarly, other growers of the world seem agonizing of the same mg/L in acetonitrile and stored at − 20 ◦ C. HPLC grade acetonitrile was
dilemma. Yang, Luo, Li, & Liu, 2016 found that 65.0% of all samples obtained from VWR CHEMICALS (Fontenay-sous-Bois France). Ethyl
analyzed of minor crops in China, mainly starfruits, crab apple, and acetate was obtained from Scharlab (Sentmenat, Spain). Phenomenex
Indian Jujube, were irregular in terms of pesticides residues detected roQ QuECHERS kit EN 15662 method packet (4.0 g magnesium sulfate,
(Yang et al., 2016). These samples contained at least one of the following 1.0 g sodium chloride, 1.0 g sodium citrate tribasic dihydrate, 0.5 g
non-authorized pesticides: carbendazim, imidacloprid, chlorbenzuron, sodium citrate dibasic sesquihydrate) and Phenomenex roQ QuECHERS
and iprodione (Yang et al., 2016). Moreover, by mean of the Article 31 of dSPE kit-15 mL CT (900 mg MgSO4, 150 mg PSA) were obtained from
Regulation (EC) No. 396/2005, Italy reported in 2017, 109 (0.9%) Torrance, USA. Topas pesticide formulation (penconazole 10% EC) was
incompliant samples with the EU Maximum Residue Limits (MRLs) out purchased from Syngenta.
of a total of 11,497 samples food samples tested. The only loquat sample
tested out of the 109 total samples had dimethoate residues exceeding 2.2. Sampling
the EU MRL (EFSA, 2019). Sangur et al., 2012 investigating pesticides
residues in fruits and vegetables in Hatay region Turkey, found car­ For the purpose of screening pesticide residues on loquat, a total of
bendazim in 30% of the tested loquat samples (Sungur & Tunur, 2012). 128 loquat samples were collected randomly over a period of 3 years
Yang et al., 2016 stated that hardships are eminent for producers from 2017 till 2019 from orchards, wholesale markets, retail shops, and
lacking authorized plant protection products with regulatory neglect packing houses of fruits meant for export.
(Yang et al., 2016). Accordingly, it would be desirable to equip the Concerning the dissipation and normal studies, sampling was carried
Lebanese farmers with registered chemical pesticides to use safely on following the FAO guidelines, “Submission and evaluation of pesticide
loquat, especially members of the triazoles family, which are known to residues data for the estimation of maximum residue levels in food and
curatively control scab. But, at the same time, because repeated uses of feed” 2016. Each sample consisted of 12 fruits of apples or the equiva­
triazoles induce resistance in scab, registering fungicides with different lent of 2 kg of apple or loquat with size and quality ready for harvesting.
modes of action to be alternatively used will help in resistance For the dissipation studies on apple and loquat, 3 field replicates were
management. taken at intervals 0 + 2 h, 1, 2, 6, 9, 14 and 21 days after the 3rd
Extrapolation of pesticides good agricultural practices (GAP) from a pesticide application. For normal studies on apple and loquat, two field
major crop to a minor crop through a reduced number of supervised field replicate samples were taken at intervals 0 + 2 h and 14 days from the
trials and bridging studies among crop groups is the main common control and the treated plots.
approach recognized by the regulatory authorities and recommended by
the Organization for Economic Co-operation and Development (OECD) 2.3. Sample preparation: QuEChERS extraction
(OECD, 2016), European Union (EUROPEAN COMMISSION, 2017) and
FAO (FAO, 2016) to tackle the problem of minor crops. To ensure a quick and easy sample treatment, a modified QuEChERS
Penconazole is a fungicide, belonging to the triazoles family, used to (quick, easy, cheap, effective, rugged and safe) method was used. This
control scab on pomefruits (apple, pear), including loquat in many parts method was originally developed as a powerful sample preparation to
of the world. Nevertheless, in Lebanon, penconazole is registered only analyze hundreds of pesticides residues in different kinds of food sam­
on apple and pear by adoption of the cGAP of Spain, without conducting ples. The whole 2 kg field samples of whole apple and Loquat fruits were
supervised field trials as it is a customary practice in Lebanese regis­ homogenized thoroughly. Ten g of the homogenized sample was
tration to follow the registration of a reference country. The Maximum weighted in a 50 mL centrifuge tube. An aliquot of 10 mL of acetonitrile
Residue Limit adopted by the EC for penconazole on pomefruits is 0.15 (ACN) was added to the sample, then hand-shaken vigorously for 1 min.
mg/kg, while that on loquat is 0.07 mg/kg (European Commission, A packet of Phenomenex roQ QuECHERS kit EN 15662 method was
2020). In Lebanon, The MRL officially adopted for penconazole on apple added to the tube, which was then sealed tightly, hand-shaken vigor­
is 0.1 mg/kg as listed in the Codex Alimentarius (FAO/WHO, 2017) ously for 1 min, then centrifuged for 5 min at 5000 rpm. A 6 mL aliquot
while no MRL for loquat has been specified. Regardless of how sound of the upper ACN layer was transferred into a Phenomenex roQ
this practice is, if there were pesticides residues trials conducted on QuECHERS dSPE kit-15 mL tube; the tube was tightly capped and hand-
apple, occupying an area of 14,300 ha and total production of 160,000 shaken for 30 s. The 15 mL tube was centrifuged for 5 min at 5000 rpm.
tons/year (Lebanese Ministry of Agriculture/FAO, 2017), then the 300 μL of the upper layer were then filtered through 0.45 μm poly­
expansion of the label to include loquat can be done by extrapolation vinylidene fluoride (PVDF) syringes filter into 1.5 mL vials, dried by N2
with a minimum number of 3 trials on loquat, as apple is the flow and reconstituted with ethyl acetate for GC analysis. Prior to

2
M.I. Abou Zeid et al. Food Control xxx (xxxx) xxx

Table 1
Location, trial type, and experimental conditions and parameters *(Meier et al., 1994),**(Martínez-Calvo et al., 1999).
Type of trial Location Start End date T (◦ C) Av. relative Variety Spray volume in L at 3rd Av. fruit Growth stage
date Humidity application weight (g) (BBCH)*,**

Apple
Dissipation Kfardebian 9/8/ 19/9/ 19–29 55–57 Red starking 60 180 81
2017 2017
Normal Aammiq 22/8/ 25/9/ 19–29 55–57 Golden 100 160 84
2017 2017 Delicious
Normal Qartaba 5/9/ 10/10/ 13–27 50–56 Super chief 16 180 89
2017 2017
Normal Qartaba 5/9/ 10/10/ 13–27 50–56 Golden 20 160 89
2017 2017 delicious
Normal Kfardebian 8/9/ 11/10/ 16–27 55–56 Scarlet spur 80 180 81
2017 2017
Normal Kfardebian 8/9/ 11/10/ 16–27 55–56 Double red 80 185 81
2017 2017
Loquat
Dissipation Zoghdraya 19/3/ 9/4/ 9–20 58–63 Baladi 85 28 807
2018 2018
Normal Darb-as- 28/2/ 2/4/ 9–20 58–63 Turkish 30 41 709
sim 2018 2018
Normal Darb-as- 28/2/ 2/4/ 9–20 58–63 Spanish 68 32 708
sim 2018 2018

injections, 9 μL of tri-phenyl phosphate (TPP) were added as injection raised at 16 ◦ C/min up to 280 ◦ C and held there for 7.2 min. The total
internal standard (I-IS). run time was 35 min. The mass spectrometer was operated with an
electron impact (EI) source in multiple reactions monitoring (MRM)
mode. The electron energy was 70 eV and the source, transfer line and
2.4. Pesticide residue determination: GCMSMS and LCMSMS
quadrupole temperatures were set at 280 ◦ C and 150 ◦ C, respectively. In
order to prevent instrument damage, the solvent delay was set at 4.5
GC-MS/MS analyses were carried out with an Agilent 7890A GC
min. The optimized parameters for penconazole are as follows: retention
equipped with 7693 Agilent Auto-sampler and 7000C Triple Quadrupole
time 18.7 min, quantitative transition 248 > 192, and qualitative tran­
GC/MS system from Agilent technologies (Santa Clara, California, USA).
sition 248 > 157. An ion ratio percentage of 30% tolerance was used for
The separation was performed on a HP-5 MS column, 0.25 mm internal
both standards and samples.
diameter × 30 m length, 0.25 μm particle size. Helium (purity 99.996%)
LC-MS/MS analyses were carried out with an Agilent 1200 HPLC
was used as a carrier gas at a constant pressure of 11 psi. The inlet
equipped with 3200 QTrap Triple Quadrupole Ion Trap system from AB
temperature was set at 250 ◦ C; the mode of inlet was splitless; the in­
Sciex. The separation was performed on an Agilent Column Zorbax
jection volume was 1 μL. The column temperature program was as fol­
Eclipse plus C18 Analytical, 4.6 mm internal diameter × 150 mm length,
lows: the initial temperature was maintained at 70 ◦ C for 1 min,
5 μm particle size. The solvents used were: Solvent A (water +20%
increased to 160 ◦ C at a rate of 50 ◦ C/min, raised to 200 ◦ C at 2 ◦ C/min,

Table 2
Chromatographic conditions, Validation and MS parameters of 14 chemical classes representative analytes out of 76.
Analyte RT (min) Q1 Q3 CE (ev) Spiked level (mg/kg) Recovery RSD (%,n = 10) Matrix effect % Correlation coefficient

Acetamipride 10.9 223 126.1 27 0.01 96.15 14.53 8.0 0.9998

223 73 75 0.05 81.88 2.86
azoxystrobin 16.1 404.1 371.9 10 0.01 96.12 13.46 6.1 0.9998
404.1 344 19 0.05 80.22 3.05
carbendazim 12.1 192.082 160.1 19 0.01 96.07 6.05 16.6 0.9997
192.082 132.2 37 0.05 78.86 9.39
chlorpyrifos 16.28 313.8 258 14 0.01 103.6 17.31 2.7 0.9998
314 286 5 0.05 82.28 4.88
cyflufenamid 24.26 188.1 88 35 0.01 74.44 18.46 1.7 0.9997
118.1 89 25 0.05 73.58 2.94
cymoxanil 11.6 199.164 127.9 13 0.01 110.41 12.13 4.5 0.9991
199.164 83 19 0.05 85 3.33
dimethoate 11.1 230.08 125.1 25 0.01 106.52 13.91 0.9 0.9998
230.08 199 13 0.05 87.22 2.57
Diflubenzuron 18.5 311.03 158.1 17 0.01 109.55 11 7.2 0.9996
311.03 141 39 0.05 87.16 5.71
flutriafol 21.15 219 123.1 12 0.01 95.6 6.43 0.7 0.9992
219 95 20 0.05 75.46 3.23
Fluazinam 20.3 466.1 173 27 0.01 92.9125 18.52 8.2 0.9997
466.1 174 29 0.05 73.28 5.16
metalaxyl 14.16 249 146 20 0.01 9.58 4.81 0.1 0.9997
160 130 20 0.05 75.4 3.14
methomyl 9.4 163 88 13 0.01 91.36 4.77 3.7 0.9999
163 106 13 0.05 77.46 4.32
myclobutanil 23.22 179 125 14 0.01 93.72 4.77 9.0 0.9997
179 152 6 0.05 81.32 5.82
pendimethalin 18.34 252.1 162.1 10 0.01 102.68 11.6 0.7 0.9994
252.1 161.2 20 0.05 76.54 5.8

3
M.I. Abou Zeid et al. Food Control xxx (xxxx) xxx

Methanol+ 5 mM Ammonium Acetate) and solvent B (Methanol + 5 mM the group representative of loquat. Performance of the used analytical
Ammonium Acetate). The injection volume was 10 μL. The total run method was evaluated by checking validation parameters and accep­
time was 30 min. The mass spectrometer was operated with an electro tance criteria, following SANCO guidelines on “ANALYTICAL QUALITY
Spraying ionisation (ESI) source in multiple reactions monitoring CONTROL AND METHOD VALIDATION PROCEDURES FOR PESTICIDE
(MRM) mode. The optimized parameters for penconazole are as follows: RESIDUES ANALYSIS IN FOOD AND FEED Nº SANTE/12682/2019”.
retention time 18.4 min, quantitative transition 284.344 > 159.1 and Linearity check was performed by plotting calibration curves of the
qualitative transition 284.34 > 69.9. An ion ratio percentage of 30% peak area against a range of 7 concentrations (0.01–0.5 mg/L) of a
tolerance was used for both standards and samples. mixture of 76 pesticides analytes in Acetonitrile with n = 10 replicates of
the target analyte. Acceptability was conditioned for correlation coef­
ficient R2≥0.98. All the correlation coefficient of the calibration curve
2.5. Trials and spraying technique on apples and loquats of the 76 analytes varied between 0.9991 and 1 demonstrating a very
good linearity (Table 2).
During the years 2017 and 2018, one dissipation and 5 normal The accuracy was assessed from the recovery of the pesticides ana­
pesticide field trials were conducted on apples in 3 different locations in lytes at 2 levels of fortification: 0.01 mg/kg and 0.05 mg/kg. The re­
Mount-Lebanon and Beqaa. In addition, one dissipation and 2 normal coveries of all tested analytes varied between the lowest 73% for
field trials were conducted on loquat in 2 different locations in East proquinazid to 112% for etoxazole at 0.01 mg/kg level, and 70.44% for
Sidon, the main area of loquat production, South Lebanon. The trials tolfenpyrad and 90.56% for etoxazole at 0.05 mg/kg level. The results
plots were managed following local agricultural practices, including indicate satisfactory method performance in terms of recovery as shown
irrigation, fertilization, pest control and other practices to ensure good in Table 2.
crop production. The Guidelines on comparability, extrapolation, group Precision of the method was evaluated by assessing repeatability and
tolerances and data requirements for setting MRLs SANCO 7525/VI/95 reproducibility through the calculation of the relative standard devia­
Rev. 10.2 September 23, 2016 and OECD guideline 509 and its Guidance tion on test results for 10 replicates at 2 spiked levels. The lowest RSD at
document on crop field trials (Series on Pesticides No. 66) were fol­ 0.01 mg/kg spiked level was calculated as 4.49 for pirimicarb, while the
lowed. A single un-replicated plot design was used. Each of the treated highest calculated was 18.52 for fluazinam. The lowest RSD calculated
and the control plots was made of 6 trees of the same variety, separated at 0.05 mg/kg was for diazinon, while the highest was for thiabendazole
by a buffer zone of, at least, 15–20 m, in commercially grown orchards. with a value of 13.04 (Table 2). All the calculated RSD for the different
All the conditions and parameters related to the field trials are sum­ analytes were less 20%, indicating a very good repeatability of the
marized in Table 1. method. As an important step in the verification process, the matrix
The same GAP adopted by Lebanon for penconazole on apples was effect was investigated by comparing calibration of pesticides analyte
followed in all the trials. It consisted of spraying thrice at 10 days in­ standards dissolved in solvent with matrix-matched standards. Per­
terval from − 20, − 10, and 0 days from sampling at a rate of 50 mL of the centage matrix effect was calculated using the following equation:
commercial formulation/100 L of water and a PHI = 14 days. At each
site, commercial application of the pesticide was simulated using the

Standard deviation between the slopes of the calib. curve in solvent and the matrix
% ME = RSD = 100*
mean of the slopes of analyte in solvent and in matrix

available spray equipment that varied between a tractor driven pump

with a hand gun in Aammiq, a motorized back sprayer in Qartaba, and The matrix effect varied between the lowest value of 0.11 for met­
most commonly used handgun attached to a portable motorized pump in alaxyl and 16.67 for carbendazim (Table 2). It is considered that there is
the rest of the trials. Before application, the spray equipment was no matrix effect if the % is ≤ 20% in accordance with SANCO guidelines.
checked for delivery rate that was recorded. For each treatment, clean
tanks with clean hoses were used to dilute and spray the fungicide 4. Results and discussion
immediately. A fine spray targeted the foliage to a thorough coverage
until dripping. No sprays were made when it was raining or when wind 4.1. Screening results of loquat samples
speed was more than 10 km/h.
Out of the 128 samples of loquat tested for pesticides residues, 51
2.6. Statistical analysis samples were contaminated (Table 3) among which 48 samples held
residues of unauthorized pesticides, indicating that the Good Agricul­
Data were statistically evaluated using Excel and IBM SPSS 22.0 tural Practices (GAP) may not be well followed in Lebanon (Yu et al.,
(statistical package for social sciences). The penconazole residues values 2017). The other 77 samples were compliant, 12 samples of which
from the dissipation studies on apple and loquat were best fitted to a contained residues of difenoconazole, the only registered pesticide on
first-order kinetics, C–– C0 e− kt, employing a nonlinear least-squares loquat in Lebanon with levels below the MRL. No residues were detected
regression analysis of residue concentration against time. To ascertain at all in the other 65 samples.
if datasets originating from apple and loquat residues come from pop­ The most frequently encountered unauthorized pesticides detected
ulations characterized by similar mean and variance, statistical tool are listed as percentage of the total number of samples tested: cyper­
(Mann-whitney U Test) was used. methrin (10.9%) with concentrations ranging from 0.021 to 0.136 mg/
kg, dimethoate (6.25%) with concentrations ranging from 0.0153 to
3. Performance of the analytical method 0.595 mg/kg, methomyl (6.25%) with concentrations ranging from
0.0162 to 0.0518 mg/kg, carbendazim (3.1%) with concentrations
Originally, validation experiments have been performed in both ranging from 0.08 to 0.0963 mg/kg, and thiametoxam (2.3%) with
LC–MS/MS and GC–MS/MS analytical systems to prove suitability of the concentrations ranging from 0.017 to 0.062 mg/kg. It is worthy to note
multi-residue analysis method to test for 76 pesticides analytes in apple, that these pesticides are now banned in Lebanon. Though cypermethrin,

4
M.I. Abou Zeid et al. Food Control xxx (xxxx) xxx

carbendazim, and thiametoxam are banned in Lebanon, their residues

0.059
levels were below the MRLs set by the EU. In contrast, methomyl and

0.01
n/a
cymoxanil
dimethoate residues levels were higher than the LOQ = 0.01 mg/kg,

1
which is the set MRL when the pesticides are disapproved in the EU.
Similar pesticides residues, with different frequencies, were detected

0.03
n/a
Thiophanate − methyl

1
within the Food and Drug Administration (FDA) pesticide residue
monitoring program fiscal year 2017 on 4270 samples of imported

0.0497
commodities and were listed as follows in percent of the total samples

n/a
0.1
tested: cypermethrin (4.7%), dimethoate (2.2%), methomyl (1.1%),
deltamethrin

1
carbendazim (7%), and thiametoxam (6%) (U.S. FDA, 2019).
Loquat is one crop that currently has no MRLs set in the Codex Ali­

0.013
n/a mentarius (FAO/WHO, 2017). Consequently, the EU data base on MRLs
myclobutanil 0.6

1
(European Commission, 2020) was used for comparison of the detected
residues levels from our survey. Pesticides encountered, such as flu­
0.012

triafol (5.4%), cyflufenamid (3.1%), chlorpyrifos (2.3%), tebuconazole

n/a
0.7

isopyrazam
1

(1.5%), tetraconazole (<1%), lambda-cyhalothrin (<1%), isopyrazam

(<1%), myclobutanil (<1%), deltamethrin (<1%), thiophanate-methyl
0.028

(<1%) are not authorized because they have never been registered for
n/a
0.2

lambda − cyhalothrin
1

use in Lebanon on loquat (Table 3). Nevertheless, their residue levels did
not surpass the EU-MRLs, and they could have been considered safe and
0.01

conforming with the standards. Other pesticides, such as: man­

n/a
1.5

metalaxyl
1

dipropamide (1.5%), azoxystrobin (1.5%), metalaxyl (<1%), and cym­

oxanil (<1%), were considered unauthorized as they were not registered
0.03
n/a
0.3

for use on loquat by the EU and their residues levels surpassed the 0.01
tetraconazole
1

mg/kg MRL.
Co-occurrence of pesticides residues is common when controlling a
0.0516
0.0549

multitude of pests as confirmed in the results of the EU monitoring

0.01

azoxystrobin
2

program on pesticides residues in human food conducted in 2016 (EFSA,

2018). Multiple residues of pesticides were found in 23 (17.9%) of the
0.0112
0.0578

128 tested samples. One sample of the 128 tested samples had up to 4
0.01

pesticides residues (mandipropamide + difenoconazole + dimethoate +

mandipropamide
2

tebuconazole). Ten (7.8%) samples included a combination of residues

of 3 pesticides (2 scab fungicides and one insecticide or 2 insecticides
0.0101
0.0947

and 1 fungicide). Twelve (9.4%) samples comprised residues of 2 pes­

0.5

tebuconazole
2

ticides: one scab fungicide and one insecticide. Similar results were
recorded by Ramadan et al. in his survey on 10 vegetables (Ramadan
0.017
0.062

et al., 2020). Four samples included the presence of technically unjus­

0.3

thiametoxam
tified residues of some pesticides, like mandipropamide or azoxystrobin,
3

co-occurring with residues of difenoconazole. This might be explained

0.028
0.391

chlorpyrifos by the fact that growers could have sprayed commercial formulations
made of 2 active ingredients because they only contained difenocona­
1

zole, disregarding the fact that these combinations included also other
irrelevant pesticides in the control of loquat pests. Other unjustifiably
0.05
0.01
0.02

cyflufenamid
4

found pesticides residues were those of cymoxanil and metalaxyl that

Comparison with EU-MRL as no Codex-Alimentarius values are listed.

are not known to control any of the common pests listed on loquat in
0.096

Lebanon. In turn, these results signal the importance of promoting

0.08

carbendazim
extension and the training of growers on the safe and effective use of
2

4
Screening results of 128 loquat samples for pesticides residues.

pesticides. Moreover, the necessity of facilitating pesticides registration

and setting MRLs on minor crops is brought in front as is the case in
0.0098
0.0693

other countries (Yang et al., 2016).

0.4

Flutriafol
7

Presence of at least one pesticide residue ≥ LOQ.

Pesticide not registered on loquat in Lebanon.

4.2. Dissipation studies

0.0162
0.0518
0.01

methomyl
51
48
24
8

The results of the dissipation trials showed that penconazole 10% EC

sprayed at the same rate of 50 ml of penconazole 10% EC/100 L of water
>MRLc
0.0153

on both apples and loquat under commercial field conditions dissipated

(European Commission, 2020).
0.595
0.01

NAb

following a first order kinetic dissipation model (Fig. 1).

dimethoate
8

The correlation coefficients varied between the 2 curves and ranged

from 0.869 to 0.966, showing a very good fit to a first order model
0.021
0.136

Contaminated samplesa

despite the variations attributed to the uncertainties concurrent with

cypermethrin
14
1

field trials. These results are in agreement with many published studies
Irregular samples

conducted on penconazole dissipation on tomatoes (Abd-Alrahman &

MAX (mg/kg)
Min (mg/kg)

Ahmed, 2012; Cabizza, Dedola, & Satta, 2012; Romeh, Mekky,

Frequency
EU-MRLd

Ramadan, & Hendawi, 2009), on other crops (Abd-Alrahman & Ahmed,

Table 3

Loquatsamplesn ​ = ​ 128 2013; Hem et al., 2011; Zhang et al., 2019), and on dissipation of other
triazoles on apples (He et al., 2016; Szpyrka & Walorczyk, 2017; Yu
d
b
a

5
M.I. Abou Zeid et al. Food Control xxx (xxxx) xxx

Fig. 1. Dissipation of penconazole on apple and loquat.

et al., 2011). below the 0.07 mg/kg MRL set by the EU, except for the trial conducted
The absolute values of the slopes (K) varied between 0.073 and on the “Baladi” variety in Zoghdrayah where the initial deposit went
0.081, showing a faster dissipation in apple compared to loquat. This way beyond the MRL (Table 4).
might be explained by the different prevailing climatic conditions, Variations in initial residue levels at 0+2 h between apple and loquat
mainly temperature, where the temperature range (9–20 ◦ C) recorded can be explained by differences in fruit size (surface to volume ratio),
during the loquat dissipation trial was relatively lower than the tem­ while variations in residue concentration at other intervals can be
perature range (19–29 ◦ C) during the apple dissipation trial (Alister, attributed to factors affecting dissipation rate, mainly: different crop
Araya, Becerra, Saavedra, & Kogan, 2017; Fantke, Gillespie, Juraske, & growth dilution or apparent dilution and different prevailing weather
Jolliet, 2014; Farha, Abd El-Aty, Rahman, Shin, & Shim, 2016; Marín, conditions.
Oliva, Garcia, Navarro, & Barba, 2003). Residue levels of penconazole at 14 days of both apple and loquat
The comparison of residue levels at 6 days with those of the initial trials were shown to belong to the same population, after conducting a
deposits in the 2 dissipation trials shows a higher dissipation of penco­ Mann-Whitney U test that revealed a p-value = 0.714 > 0.05 (the sig­
nazole in loquat (53.1%) than in apple (46.1%). nificance level). Accordingly, individual residue datasets from the 6
By the 14th day of the trials, penconazole degraded by 76% in apple trials on apple and individual data sets from the 3 trials on loquat,
and 67% in Loquat. At day 21, residues of penconazole were still reflecting the same cGAP will be compiled (FAO, 2016). Therefore,
detected at levels of 20 μg/kg in apple and 55 μg/kg in loquat but with residue data sets can be grouped and a preliminary MRL of 0.1 mg/kg
values below the values of the EU-MRL of 0.1 mg/kg set on apple and can be adopted in Lebanon at the same GAP for both apple and Loquat as
0.07 mg/kg set on loquat (Alister et al., 2014). The half-life calculated penconazole is already registered in Lebanon on apple. Nevertheless,
on apple and loquat were 8.56 days and 9.49 days respectively with a none of the loquat trials showed at 14 days residue levels of penconazole
difference of only about one day. exceeding the EU-MRL of 0.07 mg/kg. Accordingly, a preharvest inter­
val (PHI) of 14 days can be proposed for loquat with a MRL of 0.07
4.3. Normal studies mg/kg with the same GAP practiced on apple.
Farmers should not be trapped between official negligence and the
Following the GAP of Lebanon, the initial deposit (C0) of pencona­ reluctance of the suppliers to register their pesticides on minor crops
zole 10% EC on apple did not show residue levels above the adopted 0.1 because of the lack of justified return. The government should take the
mg/kg MRL set by the Codex Alimentarius, except for the trial con­ initiative to expand the registration not only of the other triazoles
ducted on the Golden delicious variety in Aammiq-Bekaa. Similarly, the already registered on apple to include loquat, but also to expand the
initial residues concentration (C0) derived from the loquat trials were registration of all the pesticides on a commodity group representative to
other minor crops in that group. Nevertheless, all of this must be done
gradually within a program of supervised field trials to set MRLs of
Table 4
registered pesticides on minor crops.
Initial residue concentrations at 0 + 2 h and 14 days.
trial # Varieties Concentration at 0 + 2 h s Concentration at 14 days
5. Conclusion
in μg/kg in μg/kg

Apple This study has identified a range of unauthorized pesticides used on

1 Golden 131 ± 20 62.5 ± 9
delicious
loquat produced in Lebanon. Presumably, the same issue is faced with
2 Super chief 59.5 ± 8 24 ± 3 other minor crops, such as berries, avocado, and persimmon. Unfortu­
3 Golden 78.5 ± 19 51.5 ± 4 nately, no pesticides are registered on these crops, which have the po­
delicious tential to be exported to markets that are more and more restrictive in
4 Scarlet spur 33.5 ± 4 12.5 ± 1
terms of pesticides residues. Furthermore, this study showed that pen­
5 Double red 61.5 ± 8 22.5 ± 1
Diss Red starking 93 ± 21 20 ± 5 conazole behaved similarly on both apple and loquat, dissipating
Loquat following 1st order kinetics. Penconazole can be proposed as a safe
6 Turkish 46 ± 2.83 22.5 ± 10.5 chemical alternative to control scab on loquat, with PHI of 14 days and a
7 Spanish 57 ± 0.014 LOQ MRL = 0.07 mg/kg, following the same GAP adopted for apple.
Diss Baladi 167 ± 50 55 ± 12
A safe chemical management on minor crops necessitates monitoring

6
M.I. Abou Zeid et al. Food Control xxx (xxxx) xxx

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