Chemosphere 93 (2013) 190–195
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Chemosphere
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Residues of cyantraniliprole and its metabolite J9Z38 in rice field
ecosystem
Changpeng Zhang 1, Xiuqing Hu 1, Hua Zhao, Min Wu, Hongmei He, Chunrong Zhang, Tao Tang,
Lifeng Ping, Zhen Li ⇑
State Key Lab Breeding Base for Zhejiang Sustainable Plant Pest Control, MOA Key Lab for Pesticide Residue Detection, Institute of Quality and Standard for Agro-Products,
Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China
h i g h l i g h t s
A method was developed to detect of cyantraniliprole and J9Z38 in rice.
The half-lives of cyantraniliprole were 3.2, 4.4 and 6.3 d in rice straw, respectively.
The recommended MRL of cyantraniliprole was 0.1 mg kg
a r t i c l e
i n f o
Article history:
Received 16 January 2013
Received in revised form 27 April 2013
Accepted 9 May 2013
Available online 22 June 2013
Keywords:
Cyantraniliprole
J9Z38
Residue
Rice
1
in brown rice.
a b s t r a c t
A simple and reliable analytical method was developed to detect cyantraniliprole (HGW86) and its
metabolite J9Z38 in rice straw, paddy water, brown rice, and paddy soil. The fate of cyantraniliprole
and its metabolite J9Z38 in rice field ecosystem was also studied. The target compounds were extracted
using acetonitrile, cleaned up on silicagel or strong anion exchange column, and analyzed by ultra-performance liquid chromatography–tandem mass spectrometry. The average recoveries of cyantraniliprole
and J9Z38 in rice straw, paddy water, brown rice, and paddy soil ranged from 79.0% to 108.6%, with relative standard deviations of 1.1–10.6%. The limits of quantification of cyantraniliprole and J9Z38 were 18
and 39 lg kg 1 for rice straw, 2.8 and 5.0 lg kg 1 for paddy water, 4.3 and 6.3 lg kg 1 for brown rice, and
3.9 and 5.3 lg kg 1 for paddy soil. The trial results showed that the half-lives of cyantraniliprole were 3.2,
4.4, and 6.3 d in rice straw and 4.9, 2.0, and 6.2 d in paddy water in Zhejiang, Hunan, and Shandong,
respectively. The respective final residues of cyantraniliprole and J9Z38 in brown rice were lower than
0.05 and 0.02 mg kg 1 after 14 d of pre-harvest interval. The maximum residue limit of cyantraniliprole
at 0.1 mg kg 1 and dosage of 100 g a.i. hm 2, which could be considered safe to human beings and animals, were recommended.
Crown Copyright Ó 2013 Published by Elsevier Ltd. All rights reserved.
1. Introduction
Cyantraniliprole (3-bromo-N-[4-cyano-2-methyl-6-[(methylamino)-hydroxy]phenyl]-1-(3-chloro-pyridine-2-yl)-1-H-pyridine-5-formamide, DPX-HGW86) is an o-amino-benzamide
insecticide in which a cyano group replaced the 4-halo substituent
of the former anthranilic diamide chlorantraniliprole (Feng et al.,
2010). The mode of action of cyantraniliprole relies on the activation
of the ryanodine receptors of insects, which are critical for muscle
contraction (Lahm et al., 2007). This activation of the ryanodine
receptors affects calcium homeostasis by unregulating the release
of internal calcium in the cell, which leads to feeding cessation, lethargy, muscle paralysis, and ultimately, death of the insect (Cordova
⇑ Corresponding author. Tel.: +86 571 86404056; fax: +86 571 86402186.
1
E-mail addresses: [email protected], [email protected] (Z. Li).
These authors equally contributed to this work.
et al., 2006; Jacobson and Kennedy, 2011). Cyantraniliprole exhibits
remarkable selectivity and low toxicity to mammals, improved plant
mobility and increased spectrum has been reported (Lahm et al.,
2009; Dong et al., 2012). Cyantraniliprole is used to control Lepidoptera pests and sucking pests in a wide range of crops (Chai et al., 2012).
Studies on analytical methods for cyantraniliprole residue have
been reported in several crops, vegetables, and environmental materials (Schwarz et al., 2011; Sergio et al., 2011; Timo et al., 2011; Dong
et al., 2012; Sun et al., 2012). However, to our knowledge, a residue
analytical method for cyantraniliprole and its metabolite J9Z38 in
rice has not been reported to date. Moreover, the maximum residue
limits (MRLs) of cyantraniliprole in rice have not been legislated in
America, European Union, or China. No study has been reported on
the fate of cyantraniliprole in rice field ecosystems.
Improper and extensive use of pesticides does not only pollute
cultivated soil and groundwater, but it also accumulates in aquatic
plants (Jiries et al., 2002; Yu and Zhou, 2005). Public concern over
0045-6535/$ - see front matter Crown Copyright Ó 2013 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2013.05.033
191
C. Zhang et al. / Chemosphere 93 (2013) 190–195
pesticide residues in food has become important in food safety. In
this work, a simple ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method was established to
detect residues of cyantraniliprole and its metabolite J9Z38 in rice
straw, paddy water, brown rice, and paddy soil. In addition, a field
study was performed to investigate the fate of cyantraniliprole in a
rice field ecosystem. This work would help the government establish the MRL of cyantraniliprole in rice and provide basic information for proper use of cyantraniliprole in pest management
strategies in rice fields to protect public health.
2. Materials and methods
2.1. Materials and reagents
The cyantraniliprole standard (purity, 99.2%), J9Z38 standard
(purity, 97.2%), and commercial formulation (10% oil suspension)
were obtained from DuPont company (USA). Acetonitrile (chromatography grade) was supplied by Burdick & Jackson (Ulsan, Korea).
Analytical grade acetonitrile, formic acid, and ammonium formate
were purchased from Shanghai Lingfeng Chemical Regent Co., Ltd.
(Shanghai, China). Silica gel columns (500 mg/3 mL) and strong anion exchange (SAX) columns (500 mg/6 mL) were purchased from
Agela Technologies (Tianjin, China).
The properties of cyantraniliprole and J9Z38 are presented in
Table 1. Standard stock solutions of cyantraniliprole (1000 mg L 1)
and J9Z38 (1000 mg L 1) were prepared in acetonitrile. The standard stock solution of cyantraniliprole/J9Z38 (10.0/20.0 mg L 1)
was then obtained through dilution with acetonitrile. The standard
solutions required to construct a calibration graph (0.5/1, 1/2, 5/10,
10/20, 50/100, and 100/200 lg L 1) were prepared from the stock
solution through serial dilution with acetonitrile. All solutions
were stored in a refrigerator in the dark at 4 °C. Observation for
3 months showed no degradation in the working standard
solutions.
2.2. Field experiment
Field experiment site A was at Yangdu Village, which is located in
Haining town, Hangzhou City, Zhejiang Province, PR China. The soil
organic matter content and pH of site A were 12.3 g kg 1 and 7.1,
respectively. Field experiment site B was at the experimental plot
of Hunan Agricultural University in Changsha City, Hunan Province.
The soil organic matter content and pH of site B were 1.2 g kg 1 and
7.8, respectively. Field experiment site C was at Yaxin Village, which
is located in Licheng town, Jinan City, Shandong Province. The soil
organic matter content and pH of site C were 21.8 g kg 1 and 6.1,
respectively. The kinetic study was carried out in six field plots, each
with an area of 30 m2. The area was divided by irrigation and drainage channels. Cyantraniliprole formulations (10% oil suspension)
were sprayed at 150 g a.i. hm 2 (1.5 times of the recommended
dose), and the untreated plots were sprayed with water as control.
Each experiment was conducted in triplicate. The representative
samples were collected at 1 h, 3, 5, 7, 14, 21, 28, 35, 42, and 60 d (rice
straw, paddy water, and paddy soil) after cyantraniliprole application. Rice straw samples (1.0 kg) were cut into pieces, mixed fully,
and collected randomly in each treatment. Paddy water samples
(500 mL) were collected randomly in each treatment. Paddy soil
samples (1.0 kg) from the top (0 cm) to 15 cm were collected and
mixed fully in each treatment. The samples were placed in a freezer
at 20 °C until analysis.
The ultimate residue field test was carried out in 12 field plots,
each with an area of 30 m2. Cyantraniliprole formulations were
sprayed at two doses, 100 g a.i. hm 2 (recommended) and 150 g
a.i. hm 2 (1.5 times of the recommended). The treated plots were
sprayed two or three times for each dose at 7 d intervals. The untreated plots were sprayed with water as control. Each experiment
was conducted in triplicate. The samples (rice straw, brown rice,
and paddy soil) were collected at intervals of 7, 14, and 21 d after
the last spray. Brown rice samples were acquired by removing the
husk of rice. The collected samples were placed in a freezer at
20 °C until analysis.
2.3. Sample preparation
2.3.1. Rice straw
Approximately 2.0 g of sample (dried rice straw) was weighed
into a 150-mL conical flask. Acetonitrile (30 mL) and water
(10 mL) were added. The mixtures were shaken vigorously for
0.5 h and then filtered. A total of 15 mL of acetonitrile was added
Table 1
Properties and MS/MS parameters for cyantraniliprole and J9Z38.
Compound
Cyantraniliprole
J9Z38
Molecular formula
Molecular weight
log Pow (22 °C)
Water solubility (mg/L, 20 °C)
Acute toxicity of rats
Cone voltage (V)
Quantification ion transition
CE1 (eV)
Qualitative ion transition
CE2 (eV)
Structure
C19H14BrClN6O2
475
1.94
14.24
Slightly toxic
20
475 ? 286
20
475 ? 444
20
C19H12BrClN6O
457
/
/
/
50
457 ? 188
30
457 ? 299
35
CE, collision energy.
192
C. Zhang et al. / Chemosphere 93 (2013) 190–195
to the sample, and the solution was shaken vigorously for 0.5 h and
filtered. The filtrate was collected and fixed to 50 mL with
acetonitrile.
The solution (0.5 mL) obtained from the above 50 mL filtrate
was diluted with 0.5 mL deionized water and then mixed fully
for purification. A silica gel column was conditioned with 2 mL acetonitrile. The obtained solution (1 mL) was loaded to the cartridge
and collected in a flask. The analytes were eluted with 1 mL acetonitrile, and the eluate was collected. The eluate was fixed to 2 mL
with acetonitrile and filtered with 0.22-lm syringe filters for
UPLC–MS/MS analysis.
2.3.2. Paddy water
Approximately 1 mL of paddy water was transferred into a 10mL centrifuge tube, and 4 mL formic acid water (pH = 2) was added
and mixed fully for purification. A SAX cartridge was conditioned
with 5 mL acetonitrile and 5 mL formic acid water (pH = 2). The obtained solution (5 mL) was loaded to the cartridge and collected.
The analytes were eluted with 3 mL acetonitrile–water (20:80, v/
v), and the eluate was collected. The eluate was fixed to 10 mL with
acetonitrile and filtered with 0.22-lm syringe filters for UPLC–MS/
MS analysis.
2.3.3. Brown rice and paddy soil
Approximately 10.0 g sample (dried brown rice or paddy soil)
was weighed into a 150-mL conical flask. Acetonitrile (30 mL)
was added. The mixtures were shaken vigorously for 1 h and then
filtered. Then, the filtrate was collected and fixed to 50 mL with
acetonitrile. The subsequent cleanup steps were identical to Section 2.3.1.
2.4. Instrumentation conditions
Chromatographic separation of cyantraniliprole and J9Z38 was
performed on a Waters Acquity UPLC system comprising a Waters
Acquity UPLC binary solvent manager, Acquity UPLC manager, and
Acquity cartridge heater, equipped with a Waters Acquity UPLC
BEH C18 column (2.1 mm 50 mm, 1.7 lm particle size; Milford,
MA, USA). The mobile phase consisted of solvent A (0.1 mM formic
acid + 0.01 mM ammonium formate aqueous solution) and solvent
B (acetonitrile, 20:80, v/v). The mobile phase solvents were distilled and passed through a 0.22-lm pore size filter before use.
The LC separation was performed by injecting 2 lL at a flow rate
of 0.20 mL min 1. The column was kept at 40 °C, and the temperature in the sample manager was set to 10 °C.
Analysis of cyantraniliprole and J9Z38 was conducted on a triple-quadrupole mass spectrometer (XEVO TQ MS, Waters, USA)
using positive electrospray ionization (ESI+) mode. The capillary
voltage and extractor voltage were set to 3.0 kV and 40 V, respectively. The source temperature and desolvation temperature were
held at 120 °C and 400 °C, respectively. The desolvation gas was
set to a flow rate of 800 L h 1. The collision gas, which was highpurity argon, was held at 0.15 mL min 1. All the parameters for
multiple reaction monitoring transitions, cone voltage, and collision energy were optimized to obtain the highest sensitivity and
resolution (Table 1). The retention times of cyantraniliprole and
J9Z38 were 0.89 and 1.09 min, respectively (Fig. 1).
3. Results and discussion
3.1. Method performance
The calibration range was linear from 0.5 lg L
(R2 = 0.9998) for cyantraniliprole and from 1 lg L
(R2 = 0.9974) for J9Z38.
1
1
to 100 lg L
to 200 lg L
1
1
The method description for sample preparation was validated
by a recovery investigation. Recovery was determined through
experiments using a fortified blank matrix with mutually independent replicates at the three concentration levels of cyantraniliprole
and J9Z38. Five determinations were carried out on the dried rice
straw, paddy water, dried brown rice, and dried paddy soil concentrations. Prior to the extraction step, the standard in acetonitrile
was added into the blank samples, followed by standing for
30 min. The fortified samples were then processed according to
the procedure described above.
The recoveries and relative standard deviations (RSDs) of cyantraniliprole and J9Z38 in the spiked samples (dried rice straw, paddy water, brown rice, and paddy soil) were listed in Table 2. The
mean recovery values of the obtained cyantraniliprole were within
the acceptable ranges of 88.8–108.6% for all matrices. The mean
recovery values of the obtained J9Z38 were 79.0–108.0% for all
matrices. The intra-day (n = 5) and inter-day RSDs (n = 15) of the
method ranged from 1.1% to 10.6% and from 3.4% to 8.1%,
respectively.
Limits of detection (LODs) for cyantraniliprole and J9Z38 were
considered to be the concentration that produced an S/N ratio of
3, and the limits of quantification (LOQs) were defined as an S/N ratio of 10. The LODs were estimated to be 5.4, 0.84, 1.3, and
1.2 lg kg 1 for cyantraniliprole and 12, 1.5, 1.9, and 1.6 lg kg 1
for J9Z38 from five replicate extractions and analyses of spiked
samples (rice straw, paddy water, brown rice, and paddy soil,
respectively) that contain cyantraniliprole and J9Z38 at low concentration levels. The LOQs that correspond to the lowest fortification level for cyantraniliprole and J9Z38 were 18, 2.8, 4.3, and
3.9 lg kg 1 and 39, 5.0, 6.3, and 5.3 lg kg 1 in rice straw, paddy
water, brown rice, and paddy soil matrices, respectively, based
on five replicates.
3.2. Kinetic study
3.2.1. Cyantraniliprole and J9Z38 residue in rice straw
The residues of cyantraniliprole in rice straw degraded from
1.8 mg kg 1 to 0.084 mg kg 1 over 21 d of treatment in Zhejiang.
The residues degraded from 0.57 mg kg 1 to 0.055 mg kg 1 over
14 d of treatment in Hunan. The residues degraded from
1.6 mg kg 1 to 0.077 mg kg 1 over 21 d of treatment in Shandong.
The average levels of cyantraniliprole residues after approximately
28 d of treatment and J9Z38 residues obtained over the testing
periods were undetectable in the rice straw samples collected in
Zhejiang, Hunan, and Shandong.
The regression line equations for the concentration (c) of cyantraniliprole in the rice straw from Zhejiang, Hunan, and Shandong
related to time (x) were c = 1.4826e 0.1283x (r2 = 0.9566), c =
0.3531e 0.1578x (r2 = 0.7758), and c = 0.9392e 0.1109x (r2 = 0.8231),
respectively, after application of 150 g cyantraniliprole a.i. hm 2.
The corresponding curves that show the dissipation rates were
plotted in Fig. 2 A. The half-lives of cyantraniliprole in the rice
straw of Zhejiang, Hunan, and Shandong were 5.4, 4.4, and 6.3 d,
respectively. The degradation rate of cyantraniliprole in rice straw
was similar to that in cucumber (2.2 d of half-lives), tomato (2.8 d
of half-lives), and pakchoi (2.9 d to 5.3 d of half-lives) (Dong et al.,
2012; Sun et al., 2012).
3.2.2. Cyantraniliprole and J9Z38 residue in paddy water
The residues of cyantraniliprole in paddy water degraded from
0.22 mg kg 1 to 0.056 mg kg 1 over 28 d of treatment in Zhejiang.
The residues degraded from 0.19 mg kg 1 to 0.013 mg kg 1 over 14
d of treatment in Hunan. The residues degraded from 0.34 mg kg 1
to 0.071 mg kg 1 over 28 d of treatment in Shandong. The residues
of J9Z38 in paddy water degraded from 0.34 mg kg 1 to
0.044 mg kg 1 over 28 d of treatment in Shandong. The average
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C. Zhang et al. / Chemosphere 93 (2013) 190–195
Fig. 1. UPLC–MS/MS chromatograms of the (A) cyantraniliprole (0.005 mg L 1) and J9Z38 (0.01 mg L 1) in standard solution, (B) blank rice straw sample, (C) rice straw spiked
at 0.50/1.0 mg kg 1, (D) blank paddy water sample, (E) paddy water spiked at 0.05/0.10 mg kg 1, (F) blank brown rice sample, (G) brown rice spiked at 0.10/0.20 mg kg 1, (H)
blank paddy soil sample, and (I) paddy soil spiked at 0.10/0.20 mg kg 1.
Table 2
Accuracy and precision of the proposed method for cyantraniliprole and J9Z38.
Analyte
Cyantraniliprole
Samples
Rice straw
Paddy water
Brown rice
Paddy soil
J9Z38
Rice straw
Paddy water
Brown rice
Paddy soil
Concentration
(mg kg 1)
Intra-day (n = 5)
Day 1
Day 2
Inter-day
(n = 15)
RSDs (%)
Day 3
Average
recoveries (%)
RSDs
(%)
Average
recoveries (%)
RSDs
(%)
Average
recoveries (%)
RSDs
(%)
0.05
0.50
1.00
0.005
0.05
1.00
0.01
0.10
1.00
0.01
0.10
1.00
97.5
89.2
88.8
91.6
108.6
104.4
94.4
95.8
103.4
90.8
90.0
102.8
2.6
5.6
5.7
4.7
4.1
1.1
10.6
6.3
3.5
9.6
8.7
3.8
100.4
92.8
92.0
90.2
97.4
97.6
91.4
92.2
101.2
93.8
92.8
100.0
4.0
5.5
3.3
8.7
6.7
5.3
5.7
5.2
5.9
8.8
4.2
1.6
98.8
93.6
90.6
93.2
98.0
100.4
89.8
93.8
97.0
92.0
89.2
97.6
5.9
4.0
5.3
3.6
7.7
4.3
2.7
5.7
5.3
7.3
5.5
2.2
4.2
5.1
4.7
5.8
7.8
4.6
7.1
5.6
5.4
8.1
6.2
3.4
0.10
1.00
2.00
0.01
0.10
2.00
0.02
0.20
2.00
0.02
0.20
2.00
92.4
80.4
79.0
98.8
108.0
98.2
91.8
100.6
102.0
91.6
97.6
104.8
8.2
2.9
4.4
8.4
2.4
4.2
8.8
5.3
3.9
5.5
9.0
4.3
95.8
90.0
88.0
101.4
97.8
100.0
93.2
98.0
95.4
93.4
96.4
99.2
9.0
3.9
3.4
3.2
5.0
3.4
1.9
1.9
3.4
6.4
1.9
4.2
98.6
86.8
86.8
97.0
100.4
102.0
95.4
95.4
96.4
95.0
93.6
103.8
4.2
5.0
3.1
5.8
5.1
4.5
3.2
3.4
5.4
4.0
2.9
4.0
7.4
6.1
5.9
6.0
5.9
4.1
5.3
4.2
5.0
5.2
5.5
4.9
levels of J9Z38 residues over the testing periods were undetectable
in the paddy water samples collected in Zhejiang and Hunan.
The regression line equations for concentration (c) of cyantraniliprole in paddy water from Zhejiang, Hunan, and Shandong re-
lated to time (x) were c = 0.1469e 0.1410x (r2 = 0.8747),
c = 0.1064e 0.3434x (r2 = 0.8255), and c = 0.1224e 0.1115x (r2 =
0.8005), respectively, after application of 150 g cyantraniliprole
a.i. hm 2. The half-lives of cyantraniliprole in paddy water of
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C. Zhang et al. / Chemosphere 93 (2013) 190–195
Fig. 2. Kinetics of cyantraniliprole in rice straw (A) and paddy water (B).
Table 3
Ultimate residue of chlorantraniliprole and J9Z38 in brown rice, rice straw and paddy soil in Zhejiang (mg kg
Dosage (g a.i. hm
2
)
100
Spraying time
2
3
150
2
3
PHI (d)
1
).
Cyantraniliprole
J9Z38
Brown rice
Rice straw
Paddy soil
Brown rice
Rice straw
Paddy soil
7
14
21
7
14
21
0.011
<0.01
<0.01
0.011
<0.01
0.010
<0.05
<0.05
<0.05
<0.05
0.095
<0.05
<0.01
<0.01
<0.01
<0.01
<0.01
0.021
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
0.21
0.12
<0.10
0.24
0.24
<0.10
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
7
14
21
7
14
21
0.023
0.016
0.010
0.041
0.022
0.012
0.12
0.063
0.075
<0.05
<0.05
0.12
<0.01
<0.01
<0.01
0.043
<0.01
<0.01
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
0.50
0.46
0.16
0.36
0.59
0.39
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
PHI, pre-harvest interval.
Zhejiang, Hunan, and Shandong were 4.9, 2.0, and 6.2 d, respectively (Fig. 2B). The half-life of J9Z38 in the paddy water of Shandong was 10.3 d (Fig. 2, Supplementary data). The degradation
rate of cyantraniliprole in the paddy water of the rice field ecosystem seemed to be faster than that of J9Z38.
3.2.3. Cyantraniliprole and J9Z38 residue in paddy soil
The residues of cyantraniliprole over the testing periods were
undetectable in the paddy soil samples collected in Zhejiang and
Hunan, except for the 1 d Zhejiang paddy soil samples
(0.023 mg kg 1). The residues of cyantraniliprole were 0.28, 0.21,
0.19, 0.18, 0.055, 0.048, and 0.032 mg kg 1 after 1 h and 1, 3, 5,
7, 14, and 21 d in Shandong paddy soil samples, respectively,
which indicated that the adsorption equilibrium of cyantraniliprole between water and soil was established over 1 d in the rice field
ecosystem. The strong adsorption of cyantraniliprole in the paddy
soil of Shandong may be due to the higher organic matter content
of the soil. The half-life of cyantraniliprole in the paddy soil of
Shandong was 6.6 d (Fig. 2, Supplementary data). The degradation
rate of cyantraniliprole in the soil of the paddy-field ecosystem was
similar to that of the vegetable-field ecosystem (9.5 d of half-life)
(Dong et al., 2012). The residues of J9Z38 over the testing periods
were undetectable in the paddy soil samples collected from Zhejiang, Hunan, and Shandong.
3.3. Ultimate cyantraniliprole and J9Z38 residue
The ultimate residues of cyantraniliprole and J9Z38 in Zhejiang
were presented in Table 3. The concentrations of cyantraniliprole
in Zhejiang were <0.01 mg kg 1 to 0.041 mg kg 1, <0.05 mg kg 1
to 0.12 mg kg 1, and <0.01 mg kg 1 to 0.043 mg kg 1 in brown rice,
rice straw, and paddy soil samples, respectively. The concentra-
tions of J9Z38 in Zhejiang were <0.02 mg kg 1, <0.10 mg kg 1 to
0.59 mg kg 1, and <0.02 mg kg 1 in brown rice, rice straw, and
paddy soil samples, respectively. The concentrations of cyantraniliprole in Hunan were <0.01 mg kg 1 to 0.070 mg kg 1,
0.098 mg kg 1
to
0.68 mg kg 1,
and
<0.01 mg kg 1
to
1
0.074 mg kg in brown rice, rice straw, and paddy soil samples,
respectively. The concentrations of J9Z38 in Hunan were
<0.02 mg kg 1 in brown rice and paddy soil samples and
<0.10 mg kg 1 in rice straw samples (Table 3, Supplementary data).
The concentrations of cyantraniliprole in Shandong were
<0.01 mg kg 1 in brown rice and paddy soil samples, and
0.075 mg kg 1 to 0.35 mg kg 1 in rice straw samples. The concentrations of J9Z38 in Shandong were <0.02 mg kg 1 in brown rice
and paddy soil samples, and <0.10 mg kg 1 to 0.18 mg kg 1 in rice
straw samples (Table 3, Supplementary data).
The ultimate residue levels of cyantraniliprole in brown rice
14 d after application were <0.01 mg kg 1 and <0.01 mg kg 1 to
0.029 mg kg 1 at the recommended dose and 1.5 times the dose
when sprayed twice, and <0.01 mg kg 1 and <0.01 mg kg 1 to
0.025 mg kg 1 at the recommended dose and 1.5 times the dose
when sprayed three times. The ultimate residue levels of J9Z38
in brown rice 14 d after application were all <0.02 mg kg 1 at the
recommended dose and 1.5 times the dose when sprayed twice
or three times. The MRL of cyantraniliprole in rice has not been
established in China. The residues of cyantraniliprole and J9Z38
in brown rice were all lower than 0.05 or 0.02 mg kg 1, respectively, when pre-harvest interval (PHI) was 14 d or 21 d at the recommended and 1.5 times the dosage under natural climatic
conditions. Therefore, two-time application of the recommended
dose (100 g a.i. hm 2) of cyantraniliprole and 14 d of PHI were
thought to be safe for the rice field ecosystem. The recommended
MRL of cyantraniliprole was 0.1 mg kg 1 in brown rice.
C. Zhang et al. / Chemosphere 93 (2013) 190–195
195
4. Conclusions
References
A rapid, simple, and sensitive method was developed to determine cyantraniliprole and J9Z38 in rice straw, paddy water, brown
rice, and paddy soil samples. The method shows satisfactory validation parameters in terms of linearity, lower limits, accuracy, and precision. The mean recoveries in rice straw, paddy water, brown rice,
and paddy soils for cyantraniliprole and J9Z38 were 79.0–108.6%,
and the intra-day (n = 5) and inter-day RSDs (n = 15) of the method
were 1.1–10.6% and 3.4–8.1%, respectively. The LOQs of cyantraniliprole and J9Z38 in the samples (rice straw, paddy water, brown rice
and paddy soil) were 2.8–18 lg kg 1 and 5.0–39 lg kg 1, respectively. The proposed analytical method was used to determine cyantraniliprole and J9Z38 residues in the rice straw, paddy water, brown
rice, and paddy soil samples. The trial results showed that the halflives of cyantraniliprole obtained after treatments were 3.2, 4.4,
and 6.3 d in rice straw and 4.9, 2.0, and 6.2 d in paddy water in Zhejiang, Hunan, and Shandong, respectively. The final residues of cyantraniliprole and J9Z38 in brown rice were lower than 0.05 or
0.02 mg kg 1, respectively. Therefore, a dosage of 100 g a.i. hm 2
was suggested. This dosage could be regarded as safe to human
beings. A 14 d interval between pesticide application and crop harvest was also determined safe. The recommended MRL of cyantraniliprole was 0.1 mg kg 1 in brown rice. These results contribute to
establish adequate monitoring of cyantraniliprole residue and its
incorporation in pest management strategies in paddy fields and
to prevent any consumer health problems.
Chai, B.S., He, X.M., Wang, J.F., Li, Z.N., Liu, C.L., 2012. Synthesis of cyantraniliprole
and its bioactivity. Agrochemical 49, 167–169 (in Chinese).
Cordova, D., Benner, E.A., Sacher, M.D., Rauh, J.J., Sopa, J.S., Lahm, G.P., Selby, T.P.,
Stevenson, T.M., Flexner, L., Gutteridge, S., Rhoades, D.F., Wu, L., Smith, R.M.,
Tao, Y., 2006. Anthranilic diamides: a new class of insecticides with a novel
mode of action, ryanodine receptor activation. Pestic. Biochem. Phys. 84, 196–
214.
Dong, F.S., Liu, X.G., Xu, J., Li, J., Li, Y.B., Shan, W.L., Song, W.C., Zheng, Y.Q., 2012.
Determination of cyantraniliprole and its major metabolite residues in
vegetable and soil using ultra-performance liquid chromatography/tandem
mass spectrometry. Biomed. Chromatogr. 26, 377–383.
Feng, Q., Liu, Z.L., Xiong, L.X., Wang, M.Z., Li, Y.Q., Li, Z.M., 2010.
Synthesis and insecticidal activities of novel anthranilic diamides
containing modified N-pyridylpyrazoles. J. Agric. Food Chem. 58,
12327–12336.
Jacobson, A.L., Kennedy, G.G., 2011. The effect of three rates of cyantraniliprole on
the transmission of tomato spotted wilt virus by Frankliniella occidentalis and
Frankliniella fusca (Thysanoptera: Thripidae) to Capsicum annuum. Crop Prot. 30,
512–515.
Jiries, A.G., Al Nasir, F.M., Beese, F., 2002. Pesticide and heavy metals residue in
wastewater, soil and plants in wastewater disposal site near Al-Lajoun Valley,
Karak/Jordan. Water Air Soil Pollut. 133, 97–107.
Lahm, G.P., Stevenson, T.M., Selby, T.P., Freudenberger, J.H., Cordova, D., Flexner, L.,
Bellin, C.A., Dubas, C.M., Smith, B.K., Hughes, K.A., Hollingshaus, J.G., Clark, C.E.,
Benner, E.A., 2007. Rynaxypyr (TM): a new insecticidal anthranilic diamide that
acts as a potent and selective ryanodine receptor activator. Bioorg. Med. Chem.
Lett. 17, 6274–6279.
Lahm, G.P., Cordova, D., Barry, J.D., 2009. New and selective ryanodine
receptor activators for insect control. Bioorg. Med. Chem. 17, 4127–
4133.
Schwarz, T., Snow, T.A., Santee, C.J., Mulligan, C.C., Class, T., Wadsley, M.P., Nanita,
S.C., 2011. QuEChERS multiresidue method validation and mass spectrometric
assessment for the novel anthranilic diamide insecticides chlorantraniliprole
and cyantraniliprole. J. Agric. Food Chem. 59, 814–821.
Sergio, C.N., James, J.S., Anne, M.P., Joseph, P.M., John, H.M., 2011. Fast
extraction and dilution flow injection mass spectrometry method for
quantitative chemical residue screening in food. J. Agric. Food Chem. 59,
7557–7568.
Sun, J.P., Feng, N., Tang, C.F., Qin, D.M., 2012. Determination of cyantraniliprole and
its major metabolite residues in pakchoi and soil using ultra-performance liquid
chromatography–tandem mass spectrometry. Bull. Environ. Contam. Toxicol.
89, 845–852.
Timo, S., Timothy, A.S., Christopher, J.S., Christopher, C.M., Thomas, C.,
Michael, P.W., Sergio, C.N., 2011. QuEChERS multiresidue method
validation and mass spectrometric assessment for the novel anthranilic
diamide insecticides chlorantraniliprole and cyantraniliprole. J. Agric. Food
Chem. 59, 814–821.
Yu, Y., Zhou, Q.X., 2005. Adsorption characteristics of pesticides methamidophos
and glyphosate by two soils. Chemosphere 58, 811–816.
Acknowledgements
This work was supported by a grant from the National High
Technology Research and Development Program of China (863 Program) (No. 2011AA100806) and the National Natural Science Foundation of China (Grant No. 21007061).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2013.05.033.