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Research Article

Received: 3 March 2021 Revised: 9 July 2021 Accepted article published: 1 August 2021 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jsfa.11474

Dissipation and dietary risk assessment of


carbendazim and epoxiconazole in citrus fruits
in China
Ying Zhang,a,b† Yong Zhou,a,c† Tingting Duan,b Abdul Kaiumd and
Xiaogang Lia*

Abstract
BACKGROUND: Carbendazim and epoxiconazole are widely applied to control anthracnose and sand bark fungal diseases in
citrus. The residues of these two fungicides in citrus and their potential risk to consumers have generated much public concern.
We therefore sought to investigate the dissipation, residue, and dietary risk assessment of carbendazim and epoxiconazole in
citrus.
RESULTS: The dissipation kinetics and residue levels of carbendazim and epoxiconazole in citrus under field conditions were
measured using dispersive solid-phase extraction and ultra-high-performance liquid chromatography–tandem mass spectrom-
etry. The citrus samples were extracted with acetonitrile and purified by primary secondary amine sorbent. The mean recover-
ies of carbendazim and epoxiconazole ranged from 86.2 to 105.6% and relative standard deviations were ≤9.8%. The half-lives
of carbendazim and epoxiconazole in whole citrus ranged from 2.0 to 18.0 days. Hazard quotient (HQ) and risk quotient
(RQ) models were applied to whole citrus for dietary exposure risk assessment based on the terminal residue test. Hazard quo-
tients ranged from 0.066 to 0.134% and RQs from 18.48 to 82.12%.
CONCLUSION: Carbendazim and epoxiconazole in citrus degraded rapidly following first-order kinetics models. The dietary risk
of exposure to both carbendazim and epoxiconazole through citrus, based on HQ and RQ, was acceptable for human consump-
tion. This study indicates scientifically validated maximum residue limits in citrus, which are currently lacking for epoxiconazole
in China.
© 2021 Society of Chemical Industry

Supporting information may be found in the online version of this article.

Keywords: citrus; carbendazim and epoxiconazole; digestion dynamics; risk assessment

INTRODUCTION for preventing anthracnose and resin disease on citrus (i.e., with
As a citrus-producing country, China had 181 625 ha of planting the approval of a government agency). As fungal resistance often
area in 2019, with an output of 5.87 million tons of citrus fruits, limits the repeated use of a single fungicide,11 the combination of
accounting for more than one-third of the world's total output
(http://www.fao.org/faostat/en/#data/QC/visualize). Citrus is rich
in vitamins and fruit acids, which help to prevent oxidation and * Correspondence to: X Li, College of Plant Protection, Hunan Agricultural
delay aging.1,2 However, citrus is harmed by anthracnose University, Southern Regional Collaborative Innovation Center for Grain and
and sand bark, which cause epidermal scars, fruit rot, and fruit Oil Crops, 1 Nongda Road, Furong District, Changsha, 410128, China.
dropping and can affect the entire orchard, resulting in serious E-mail: lxgang@hunau.edu.cn
consequences for citrus quality and yield.3 Fungicides have †
The authors Ying Zhang and Yong Zhou contributed equally to this paper.
become the most effective and economical strategy to control
plant diseases.4,5 However, the negative effect of excessive pesti- a College of Plant Protection, Hunan Agricultural University, Southern Regional
cide residues has raised concerns internationally.6-8 Collaborative Innovation Center for Grain and Oil Crops, Changsha, China
Carbendazim, methyl benzimidazol-2-ylcarbamate, is a sys- b Institute of Plant Protection, Guizhou Academy of Agricultural Sciences, Gui-
temic, broad-spectrum benzimidazole fungicide with protective yang, China
and curative actions. Carbendazim can prevent citrus anthracnose
during planting and prevent fruit rot after harvest.9,10 Epoxicona- c Institute of Biotechnology, Hunan Academy of Agricultural Sciences, Chang-
sha, China
zole, (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophe-
nyl)propyl]-1H-1,2,4-triazole, is a triazole fungicide that inhibits d Department of Agricultural Chemistry, Sher-e-Bangla Agricultural University,
the bacterial synthesis of ergosterol and is a registered product Dhaka, Bangladesh
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www.soci.org Y Zhang et al.

carbendazim and epoxiconazole can improve the control of these five experimental plots with three orange trees and three repli-
diseases and reduce fungal resistance. Both fungicides are persis- cates for each treatment. Buffer zones were set between the plots.
tent in the environment and plant tissues, especially epoxicona- The experimental samples were collected at 2 h and then 1, 2, 3, 5,
zole, which has a half-life of 353 days in soil.12,13 Moreover, 7, 10, 14, 21, and 30 days after a dispersible form of 40%
carbendazim has reproductive toxicity in higher animals, and carbendazim-epoxiconazole suspension concentrate had been
epoxiconazole is an endocrine disruptor.14 Both have been sprayed at 300 mg of active ingredient per kilogram (1.5 times
detected frequently in fruits, which increases the risk of exposure the maximum recommended dosage). Oranges were sampled
to consumers. randomly, and the sample size was approximately 2.0 kg per treat-
A few studies have reported methods of extraction and purifica- ment replicate.
tion of carbendazim and epoxiconazole from citrus15 and orange To investigate the terminal residue levels of epoxiconazole and
juice.16 Many studies have analyzed the dissipation of carbenda- carbendazim, a low dose level of 200 mg kg−1 (recommended
zim in a variety of matrix samples such as mango,17,18 Panax noto- high dosage) and a high-dose level of 300 mg kg−1 (1.5 times
ginseng,19 pomegranate fruits,20 tea,21 and celery.22 Safety risk the recommended high dosage) were applied to the final residual
assessment of carbendazim has also been carried out for experimental plots during the early stages of half citrus by a por-
mango,17 tea,21 celery,22 and vegetables.23 As for epoxiconazole, table sprayer three or four times with an interval of 7 days. Orange
a few studies have assessed dissipation in rice paddy24,25 and samples (2 kg) were collected from each plot at 7, 14, and 21 days
wheat straw,26 and a safety risk assessment has been conducted after the last application. Sampling was performed by randomly
for wheat grains.26 However, as far as we know, there is neither collecting citrus from untreated plots. All samples were stored in
a method for determining the epoxiconazole level in citrus nor a a cooling chamber at −20 °C before further analysis.
report on the risk analysis of epoxiconazole and carbendazim in
citrus. Ultra-high-performance liquid chromatography–tandem
mass spectrometry (UHPLC–MS/MS) analysis
The purpose of our study was to establish an efficient, accurate,
and reliable method that could simultaneously detect carbenda- A UHPLC–MS/MS system, which consisted of a UHPLC (ACCECA)
zim and epoxiconazole. Field experiments were conducted to and a triple-quadrupole mass spectrometer (TSQ Endura) operat-
study the dissipation kinetics and terminal residue levels of car- ing in the electrospray ionization (ESI) mode (Thermo Fisher Sci-
bendazim and epoxiconazole in citrus and soil. Finally, the dietary entific, San Jose, CA, USA), was used to detect carbendazim and
risks of carbendazim and epoxiconazole were evaluated based on epoxiconazole. The chromatographic separation of carbendazim
terminal residue and toxicological data. This study can guide the and epoxiconazole was performed using a Hypersil GOLD octade-
safe use of pesticides and food safety assessment. cylsilane (C18) column (100 mm × 2.1 mm, 1.9 μm, Thermo Fisher
Scientific, San Jose, CA, USA) at 35 °C with a 10 μL injection vol-
ume. The mobile phase consisted of (A) ultra-pure water (contain-
MATERIALS AND METHODS ing 0.1% formic acid) and (B) acetonitrile (containing 0.1% formic
Chemicals and reagents acid), and the flow rate of the mobile phase was 0.3 mL min−1. The
Carbendazim (99.0% purity) and epoxiconazole (98.7% purity) elution steps were as follows: 20% of solvent B from 0 to 0.5 min,
were purchased from Beijing Qinchengyixin Technology Co., Ltd 20–95% from 0.5 to 2.5 min, 95% from 2.5 to 4.5 min, 95–20% from
(Beijing, China). A 40% epoxiconazole-carbendazim suspension 4.5 to 4.6 min, and 20% for 0.9 min.
concentrate (20% epoxiconazole and 20% carbendazim) was pro- The mass spectrometer was operated in the positive electro
vided by Shanghai Shengnong Pesticide Co., Ltd (Shanghai, spray ionization (ESI+) mode with selected reaction monitoring
China). Analytical grade acetonitrile, methanol, anhydrous mag- (SRM). Nitrogen was used as a sheath and auxiliary gas (pressure,
nesium sulfate, and sodium chloride were purchased from Kermel 40 psi and 10 psi, respectively). The capillary temperature and
Chemical Reagent Co., Ltd (Tianjing, China), and high- vaporizer temperatures were 320 and 350 °C, respectively. The
performance liquid chromatography (HPLC)-grade methanol spray voltage was 3.5 kV. The cycle time was 0.5 s. Based on
was purchased from Merck (Darmstadt, Germany). Ultra-pure European Union (EU) guidelines for the confirmation of com-
water was prepared using a Milli-Q system purchased from Milli- pound identification,6 two SRM transitions for each analyte were
pore (Bedford, MA, USA). Primary secondary amine (PSA, 40 μm) monitored. For carbendazim, the transition used for quantification
and 0.22-μm nylon syringe filters were purchased from Agela was 192.1 → 160.1, and the qualitative transition at 192.1 → 132.1
Technologies Inc. (Beijing, China). was used for confirmation when the RF-Lens was 90 V and the
Standard stock solutions (100 mg L−1) of carbendazim and SRM collision energy was set to 18 and 30 V, respectively. For epox-
epoxiconazole were prepared in HPLC-grade methanol iconazole, the transition used for quantification was 329.9 → 121.1,
and stored at −20 °C. The working solutions were prepared by and the qualitative transition at 329.9 → 101.1 was used for confir-
serial dilution of the stock solution to 0.0005, 0.005, 0.01, 0.05, mation when the RF-Lens was 127 V and the SRM collision energy
0.1, 0.5, 1.0, and 10 mg L−1 with acetonitrile and water (1:1, v/v) was set to 21 and 43 V, respectively.
and were stored at 4 °C before use.
Sample preparation procedure
Field trials The citrus pulp and whole-citrus samples were collected from the
Field trials were carried out in Zhangjiajie city, Hunan province; field experiments, chopped and homogenized by high-speed
Nanning city, Guanxi province, and in Wenzhou city, Zhejiang homogenization. These samples were stored at −20 °C before
province in China in 2016 and 2017. The trials were conducted fol- being analyzed.
lowing the guidelines of Good Agricultural Practice (GAP) and the First, 5.0 ± 0.1 g of blank citrus pulp and citrus samples were
‘Standard Operation Procedures on Pesticide Registration Residue weighed into 50-mL Teflon centrifuge tubes. The recovery study
Field Trials,’ issued by the Ministry of Agriculture of the People's was performed by spiking each matrix with the epoxiconazole
Republic of China.27 Each experimental location was divided into and carbendazim standard solutions. The tubes were vortexed
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Figure 1. Ultra-high-performance liquid chromatography–tandem mass spectrometry SRM chromatograms of carbendazim and epoxiconazole
(50 μg L−1) in two sample solvents. (a) Sample solvent, acetonitrile; (b) Sample solvent, 1:1 (v/v) acetonitrile/water.

for 1 min and left to stand for 30 min at room temperature to degradation rate constant (k) and half-life (T1/2). These are defined
ensure that the fungicide was distributed evenly. Then, 20 mL by Eqns (1) and (2):
acetonitrile was added to all samples. The sample tubes were
shaken vigorously for 10 min and allowed to stand for 30 min. C =C 0 e−kt ð1Þ
Subsequently, 7 g NaCl was added, and the solution was immedi-
T 1=2 = ln2  k ð2Þ
ately vortexed vigorously for 1 min and centrifuged for 5 min at
2240×g. Then, 2.0 mL of the upper layer was transferred to 5.0
where C0 and C represent the concentrations of the carbendazim
mL d-SPE tubes containing 100 mg PSA and 400 mg MgSO4.
and epoxiconazole at initial time and time t separately.
The tubes were vortexed for 60 s and then the centrifugation
The terminal residue data from whole citrus were used for the
was repeated. Then, 1.0 mL of supernatant was evaporated to
dietary risk assessment. The hazard quotient (HQ) and risk quo-
near-dryness with a nitrogen evaporator at 35 °C. The residue
tient (RQ) models were applied to evaluate the dietary risk for car-
was dissolved in 2.0 mL acetonitrile and ultra-pure water (1:1,
bendazim and epoxiconazole in citrus. For the HQ model, the
v/v) and passed through a 0.22-μm nylon syringe filter for
estimated daily intake (EDI) and the HQ were calculated using
UHPLC–MS/MS analysis.
Eqns (3) and (4):29

Method validation EDI ðmg=kg bw Þ =HR ðmg=kgÞ × food consumption ðkg=day Þ=bw
The method was validated according to the European Union
ð3Þ
SANTE/12628/2019 regulatory guidelines.28 Several parameters
including selectivity, linearity, sensitivity, accuracy, and precision HQ =NESTI=ADI×100% ð4Þ
were evaluated. Selectivity was examined by analyzing the blank
samples to confirm whether the interference peak was observed where HR is the highest residual of carbendazim or epoxiconazole
around the retention time of the analyte. To ascertain linearity, stan- in the terminal residues plot; food consumption is the average
dard solutions were analyzed in triplicate at seven concentration daily consumption of fruits by the general population; bw is the
levels (0.5, 1, 10, 50, 100, 500, and 1000 μg L−1). The parameters of average bodyweight of a Chinese adult (63 kg); NESTI is the
the linear regression equations that were obtained (peak area versus national estimated short-time intake, and ADI (milligrams per kilo-
concentration), including slope, intercept, and coefficients of deter- gram bodyweight) is the acceptable daily intake, which was set by
mination (R2), were calculated. The limit of quantification (LOQ) is GB-2763-2019 China.
the lowest concentration validated with acceptable recovery. For the long-term dietary risk assessment model, the RQ was cal-
culated using Eqns (5) and (6):
Data analyses
NEDI = fΣðSTRMi × F i Þg=bw ð5Þ
The dissipation kinetics of carbendazim and epoxiconazole in cit-
rus pulp and citrus were modeled by single first-order kinetics. RQ = NEDI=ADI × 100% ð6Þ
Origin2018 was used to fit the curve and calculate the

Table 1. Recovery (%) and RSD (%) for carbendazim and epoxiconazole from whole citrus and citrus pulp at three spiked levels (n = 5)

Spiked level, 0.002 mg kg−1 Spiked level, 0.2 mg kg−1 Spiked level, 2.0 mg kg−1

Pesticide Matrix Recovery RSD Recovery RSD Recovery RSD

Carbendazim Whole citrus 93.6 6.7 99.6 5.2 93.7 6.0


Citrus pulp 81.9 7.8 86.2 6.2 90.7 3.2
Epoxiconazole Whole citrus 105.6 9.8 103.1 4.5 97.2 5.6
Citrus pulp 92.0 9.4 91.5 6.7 93.9 3.8
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Figure 2. Typical UHPLC–MS/MS SRM chromatograms of carbendazim and epoxiconazole from a (a) 0.5 μg L−1 a standard solution of carbendazim and
epoxiconazole, (b) whole-citrus blank sample, (c) whole-citrus sample spiked at 2 μg kg−1 carbendazim and epoxiconazole, and (d) field whole-citrus
sample.

where STMRi is the median residue from the i-th supervised trial, rate of 0.3 mL/min and obtained an excellent peak shape and high
and Fi (kilograms) is the dietary consumption of the i-th grade sensitivity (Fig. 1(b)).
agricultural products for different groups of people in China. If
no STMR data were available, the corresponding maximum resi- Matrix effects, linearity, and LOQs
due limit (MRL) was used instead of STMR. HQ or RQ ≤100 means The matrix effects were investigated by comparing the MS
there is no risk or an acceptable risk, whereas HQ or RQ >100 responses from standard solutions of carbendazim and epoxico-
means there is an unacceptable chronic risk. nazole with those from whole citrus and citrus pulp matrix
extracts containing added carbendazim and epoxiconazole at
0.5, 1, 10, 50, 100, 500, and 1000 μg L−1. The resulting slope ratios
RESULTS AND DISCUSSION ranged from 0.89 to 1.08 (matrix effect was considered to be
Validation of the method ignorable if the slope ratio was between 0.8 and 1.2).35 Therefore,
UHPLC optimization parameters we used standard solutions in 1:1 (v/v) acetonitrile/water to estab-
In reversed-phase HPLC, peak deformation, peak area variation, and lish calibration curves for the analysis of the citrus samples.
reduced column efficiency, which are known as solvent effects, may The calibration curves equations in the range of 0.5–
occur when the ability of the sample solvent to dissolve the sample is 1000 μg L−1 were y = 56 583x + 389 707 and y = 9093.1x
stronger than that of the mobile phase.30,31 When acetonitrile was + 180 671 with R2 values of 0.9995 and 0.9946 for carbendazim
the sample solvent, there was a problematic solvent effect that led and epoxiconazole, respectively. The LOQs, which are defined as
to splitting of the carbendazim peak (Fig. 1(a)). When we added the minimum spiking level, were 2 μg kg−1 for carbendazim and
water to the sample solvent, the peak shapes of carbendazim epoxiconazole in whole citrus and citrus pulp.
improved and the mass spectrometry (MS) response increased as
the ratio of acetonitrile to water approached 1:1 (v/v). Thus, we ulti- Accuracy and precision
mately selected 1:1 (v/v) acetonitrile/water as the sample solvent. We conducted recovery assays of whole citrus and citrus pulp
The composition of the mobile phase was adjusted and optimized with three different concentrations of carbendazim and epoxico-
to achieve a better peak shape, retention behavior, and higher MS nazole (2, 200, and 2000 μg kg−1) to investigate the accuracy and
response of the analyte.32 In ESI+ mode, aqueous formic acid can precision. We calculated the mean recovery (%) and relative stan-
protonate the target compound and improve the response as com- dard deviation (RSD) for spiked samples, using the external
pared with ultra-pure water.33,34 We used 0.1% (v/v) formic acid in standards for quantification. Mean recovery of carbendazim from
acetonitrile and 0.1% (v/v) formic acid in ultra-pure water as the whole citrus and citrus pulp ranged from 86.2 to 99.6%, and the
mobile phase for separation of carbendazim and epoxiconazole, RSD ranged from 3.2% to 7.8% (Table 1). The recovery of epoxico-
respectively, over a Hypersil GOLD C18 column at a constant flow nazole in whole citrus and citrus pulp was 91.5 to 105.6%, with a
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Figure 3. Digestion dynamic curve of carbendazim and epoxiconazole in whole citrus.

Table 2. Dissipation dynamics parameters of carbendazim and epoxiconazole in the whole citrus

Years Compounds Locations Dynamic equations Half-life (d) Initial deposits (mg kg−1) Adj. R2

2016 Carbendazim Hunan Ct =0.20582e-0.35108x 2.0 0.205 0.92025


Zhejiang Ct =0.26556–0.34881x 2.0 0.280 0.85922
Guangxi Ct =0.17184e-0.03851x 18.0 0.225 0.90953
Epoxiconazole Hunan Ct =0.32367e-0.105x 6.6 0.493 0.75756
Zhejiang Ct =0.27005e-0.10988x 6.3 0.393 0.80496
Guangxi Ct =0.08089e-0.04338x 16.0 0.092 0.92097
2017 Carbendazim Hunan Ct =0.16712e-0.35188x 2.0 0.165 0.8993
Zhejiang Ct =0.27647e-0.33634x 2.1 0.281 0.9301
Guangxi Ct =0.10566e-0.08239x 8.4 0.127 0.86238
Epoxiconazole Hunan Ct =0.19351e-0.08708x 8.0 0.301 0.70823
Zhejiang Ct =0.32307e-0.1122x 6.2 0.451 0.80495
Guangxi Ct =0.10766e-0.07048x 9.8 0.125 0.91925

RSD of 3.8–9.8% (Table 1). The chromatograms of the blank Dissipation dynamics of carbendazim and epoxiconazole
whole-citrus pulp sample and the spiked whole-citrus pulp sam- in whole citrus
ple are shown in Fig. 2(b) and (c). These values satisfy the criteria The residue levels in the whole-citrus samples 2 h after fungicide
of the European Union SANTE/12628/2019, i.e., recovery ranging application ranged from 0.127 to 0.281 mg kg−1 for carbendazim
from 70 to 120% and RSD values of ≤20%.28 Our method is there- and 0.092 to 0.493 mg kg−1 for epoxiconazole in 2016 and 2017.
fore acceptable for the quantification of carbendazim and epoxi- The residue levels decreased gradually over time, declining by
conazole in the whole citrus and citrus pulp samples obtained more than 80.2% for carbendazim and 90.1% for epoxiconazole
from field, farms, and stores. after 30 d. The degradation kinetics of the two compounds in
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Figure 4. The terminal residue levels of carbendazim and epoxiconazole in whole citrus (a) and citrus pulp (b).

Table 3. The acceptable daily intake (ADI) (mg kg−1 bw day−1), the residue (mg kg−1), hazard quotient (HQ) (%), supervised trials median residue
(STRM) (mg kg−1), and risk quotient (RQ) (%) of carbendazim and epoxiconazole in whole citrus at different preharvest intervals (PHIs)

Pesticide ADI PHI Residues HQ STRM RQ

Carbendazim 0.03 7 0.024–0.365 0.92 0.066 82.12


14 0.025–0.195 0.49 0.026 82.02
21 0.005–0.093 0.23 0.017 82.00
Epoxiconazole 0.02 7 0.029–0.403 1.52 0.134 18.91
14 <0.002–0.126 0.48 0.058 18.63
21 <0.002–0.066 0.25 0.017 18.48

whole citrus under field conditions are given in Fig. 3. The dissipa- The residue level of epoxiconazole in citrus pulp at 14 days and
tion dynamics for carbendazim and epoxiconazole in whole citrus 21 days (<0.002–0.015 mg kg−1) was much lower than the MRL
were fitted to the first-order kinetic equation; the regression coef- value of 0.05 mg kg−1 as set by the EU, which is the only
ficients of the dynamic equations were 0.70823 and 0.9301, with MRL value in the world for epoxiconazole in citrus fruits. However,
half-lives of 2.0 days and 18.0 days, respectively (Table 2). The dif- the residue levels of epoxiconazole in whole citrus at the interval
ference in half-life values among Guangxi, Zhejiang, and Hunan of 14 days (<0.002–0.126 mg kg−1) and 21 days (<0.002–
might be influenced by different local climate conditions. 0.066 mg kg−1) were higher than 0.05 mg kg−1, indicating a pos-
Several studies have calculated the half-lives of carbendazim in sible risk of exposure to consumers.
mango,17,18 Panax notoginseng,19 pomegranate fruits,20 tea,21 and
celery22 with half-lives of 1–36.67 days and epoxiconazole in rice Dietary exposure risk assessment
paddy24,25 and wheat straw26 with half-lives of 2.9 and 39 days, The dietary risk of carbendazim and epoxiconazole exposure in
respectively. These differences may be partially due to different citrus was estimated using the main dietary data. Because there
crop varieties, different application doses, and different local are no dietary data for citrus pulp, we calculated only the dietary
climates. exposure risk for the whole citrus. The calculated HQs ranged
from 0.23 to 0.92% for carbendazim and 0.25 to 1.52% for epoxi-
Terminal residue levels of carbendazim and epoxiconazole conazole (Table 3), are much less than 100%. The potential health
in citrus risk of the two fungicides in whole citrus is acceptable.
The terminal residue levels of carbendazim and epoxiconazole in The RQ is more comprehensive because it takes into account
whole citrus and citrus pulp are shown in Fig. 4. Residue amounts the whole diet, rather than just citrus. The RQs (18.48–82.12%)
in whole citrus were 0.005–0.365 mg kg−1 for carbendazim and were still below 100% (see Table 3, and also Tables S1–S7 in the
<0.002 mg kg−1) to 0.403 mg kg−1 for epoxiconazole. The resi- supporting information), indicating that carbendazim and epoxi-
dues in citrus pulp were <0.002–0.374 mg kg−1 for carbendazim conazole do not cause unacceptable risks to the health of the gen-
and <0.002–0.132 mg kg−1 for epoxiconazole. eral population. The RQs were much higher than the HQs due to
For carbendazim, in both whole citrus and citrus pulp, residue the increased dietary risks of other crops.
amounts at 14 days and 21 days were all lower than the MRL of
various regulating agencies for carbendazim in citrus (EU,
0.2 mg kg−1; CAC, 1.0 mg kg−1; Japan, 3.0 mg kg−1; China, CONCLUSION
5 mg kg−1). We therefore suggest that14 days is an appropriate We investigated the dissipation, terminal residue levels, and
preharvest interval (PHI) for carbendazim in citrus. potential risks to human health of carbendazim and
6

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Carbendazim and epoxiconazole in citrus fruits www.soci.org

epoxiconazole in citrus. The half-lives were in the range of 2 to metabolite carbendazim residues in soil and citrus by QuEChERS-
18 days in whole citrus. The final residue levels in whole citrus liquid chromatography-tandem mass spectrometry. Chin J Chroma-
togr 35:620–626 (2017).
were much higher than those in whole pulp. The HQs ranged from 16 Razzino CA, Sgobbi LF, Canevari TC, Cancino J and Machado SAS,
0.066 to 0.134%, and RQs ranged from 18.48 to 82.12%, which Sensitive determination of carbendazim in orange juice by elec-
indicated an acceptable risk of carbendazim and epoxiconazole trode modified with hybrid material. Food Chem 170:360–365
exposure in citrus for consumers. This study thus provides basic (2015).
data for the safe use and MRLs of epoxiconazole in citrus. 17 Ahila Devi P, Paramasivam M and Prakasam B, Degradation pattern
and risk assessment of carbendazim and mancozeb in mango fruits.
Environ Monit Assess 187:4142 (2015).
18 Bhattacherjee K, Pandey BK and Prakash O, Persistence and dissipation
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This research was supported by the Natural Science Foundation of applications. J Food Sci Technol 46:347–349 (2009).
19 Wu JL, Wei HD, Sui XF, Lin J, Wang TY, Fen GG et al., Dynamics of car-
Guizhou Province (qian [2015]2101). The authors declare no com- bendazim residue in Panax notoginseng and soil. Bull Environ Con-
peting financial interests. tam Toxicol 84:469–472 (2010).
20 Mohapatra S and Lekha S, Residue level and dissipation of carbenda-
zim in/on pomegranate fruits and soil. Environ Monit Assess 188:
SUPPORTING INFORMATION 406 (2016).
21 Zhou L, Jiang YP, Lin Q, Wang X, Zhang XZ, Xu J et al., Residue transfer
Supporting information may be found in the online version of this and risk assessment of carbendazim in tea. J Sci Food Agric 98:5329–
article. 5334 (2018).
22 Chen LP, Wu CX, Xu MF, Cang T, Wang XQ, Zhao XP et al., Assessment of
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