Food Additives & Contaminants: Part A

ISSN: 1944-0049 (Print) 1944-0057 (Online) Journal homepage: http://www.tandfonline.com/loi/tfac20

Validation and quantification of neonicotinoid

insecticide residues in rice whole grain and rice
straw using LC-MS/MS

S. Karthikeyan, A. Suganthi, K. Bhuvaneswari & J. S. Kennedy

To cite this article: S. Karthikeyan, A. Suganthi, K. Bhuvaneswari & J. S. Kennedy (2019):

Validation and quantification of neonicotinoid insecticide residues in rice whole grain and rice straw
using LC-MS/MS, Food Additives & Contaminants: Part A, DOI: 10.1080/19440049.2018.1562229

To link to this article: https://doi.org/10.1080/19440049.2018.1562229

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FOOD ADDITIVES & CONTAMINANTS: PART A
https://doi.org/10.1080/19440049.2018.1562229

Validation and quantification of neonicotinoid insecticide residues in rice whole

grain and rice straw using LC-MS/MS
S. Karthikeyan , A. Suganthi, K. Bhuvaneswari and J. S. Kennedy
Department of Agricultural Entomology, Tamil Nadu Agricultural University, Coimbatore, India

ABSTRACT ARTICLE HISTORY

An efficient analytical method was developed and validated using a modified QuEChERS method Received 22 August 2018
Accepted 10 December 2018
and LC-MS/MS for the detection and quantification of neonicotinoid insecticide residues in rice
whole grain and rice straw. The samples were extracted using acetonitrile and cleaned up by KEYWORDS
dispersive solid-phase extraction. Validation based on five fortification levels showed good Rice whole grains; rice straw;
recoveries of neonicotinoids ranging from 75% to 116 % and 60% to 105 % for rice whole neonicotinoids; residue; LC-
grain and straw, respectively. The precision ranged between 3% and 17 %, and 2% and 10 % for MS/MS
grain and straw, respectively. The limit of detection was from 0.007 to 0.0084 mg kg−1 and 0.005
to 0.15 mg kg−1 and the limit of quantification was in the range of 0.024–0.028 mg kg−1 and
0.016–0.051 mg kg−1 for rice whole grain and rice straw, respectively. Monitoring of farm gate
samples indicated that, out of 24 samples, 1 rice whole grain sample was contaminated with
thiamethoxam residues (0.07 mg kg−1).

Introduction pesticides indiscriminately from nursery to har-

vest. Among them, neonicotinoids are the most
Rice (Oryza sativa) is an annual grass that belongs
effective broad-spectrum insecticides widely used
to the family Gramineae. It is a staple food in
against sucking pests (Matsuda et al. 1998;
many countries particularly in South East Asia.
Yamamoto et al. 1998; Tomizawa et al. 2000;
India has the world’s largest rice cultivated area
Tomizawa and Casida 2003). Neonicotinoid insec-
with 44 million hectare and contributes nearly
ticides are a relatively new class of pesticides with
a quarter of the world’s rice production (Van
a novel mode of action. They act as agonists at the
Hoed et al. 2006; Li et al. 2015; Mishra et al.
insect nicotinic acetylcholine receptors, which play
2018). Worldwide, rice is grown mostly under
an important role in synaptic transmission in the
submerged conditions and is harvested as covered
central nervous system (Jeschke and Nauen 2005;
grain in which the endosperm is encased in a husk
Zhang et al. 2012; Kundoo et al. 2018). In 2005,
or hull (Srikaeo 2014). Harvested rice is com-
neonicotinoids had gained a market share of 16%
monly known as rough or paddy rice (Borresen
from a total market of €7.162 billion, mainly at the
and Ryan 2014). Generally, the warm and humid
expense of organophosphorus pesticides (25%)
micro-climate prevailing in rice fields favours
and carbamates (10%) (Elbert et al. 2008).
attack by insect pests from planting to harvest
Neonicotinoid pesticides such as imidacloprid,
time (Guo et al. 2018).
thiamethoxam, acetamiprid, thiacloprid and
More than 70 insect species have been recorded
clothianidin are commonly used by Indian farm-
as rice pests and are the major constraints on crop
ers (Suganthi et al. 2018) and have gained in
yields causing serious reduction in production and
popularity. Paddy farmers depend on these neoni-
productivity. Particularly, sucking pests are the
cotinoid compounds for the management of leaf
most devastating as they not only cause direct
hoppers, plant hoppers and other sucking pests.
losses but also act as vectors for various plant
However, residues of several pesticides have been
pathogens (Guo et al. 2018; Yadav et al. 2018).
reported in rice due to indiscriminate use,
To combat this, farmers use a wide variety of

CONTACT S. Karthikeyan karthickacri@yahoo.com Tamil Nadu Agricultural University, Coimbatore, Tamil Nadu 641003, India
© 2018 Taylor & Francis Group, LLC
2 S. KARTHIKEYAN ET AL.
affecting the quality of rice and threatening public
health and the environment (Hamsan et al. 2017;
Hladik et al. 2018). In India, rice is the most
consumed cereal; eaten cooked and also as pro-
cessed products such as puffed rice, popped rice
and flaked rice. Though more focus is given on
residues in grain, their presence in straw goes
neglected. Paddy straw is being used as major
livestock fodder in the whole of South India,
although it is mainly composed of cellulose, hemi-
celluloses and lignin (Yang et al. 2007; Matano
et al. 2014). Livestock are the main source of
proteins and minerals as meat and milk for the
Indian subcontinent (Randolph et al. 2007;
Lammers et al. 2009). Straw may be one of the
routes of exposure of animals to pesticides.
Already, neonicotinoid residues have been
reported in the nestlings of Eurasian eagle owl
(Taliansky-Chamudis et al. 2017) and also in
honey (Mitchell et al. 2017).
Thus, monitoring pesticide residues in rice
whole grain and rice straw is imperative as far as
public human health is concerned. Several studies
have reported the methodologies for determina-
tion of neonicotinoids in honey, food grain, fruit
and vegetables (Takatori et al. 2008; Mastovska
et al. 2009; Kamel 2010; Liu et al. 2010).
However, few reports are available on methodol-
ogies for the determination of neonicotinoids in
rice grain, rice hull and rice straw (Zhang et al.
2017). In this study, attempts were made to sim-
plify the extraction and clean up procedures from
an existing method. Particularly, to our knowl-
edge, no studies have been reported for multi-
residue analysis of neonicotinoids in rice whole
grain and rice straw using LC-MS/MS. Hence,
this study was undertaken to develop a method
for the analysis of neonicotinoid insecticide resi-
dues using a modified QuEChERS method in rice
whole grain and rice straw and to determine the
residues in farm-collected samples.
Materials and methods
Certified pesticide standards (>90%) of acetami-
prid, thiamethoxam, thiacloprid, imidacloprid,
and clothianidin, and solvents and reagents
including acetonitrile and formic acid of MS
grade were obtained from Sigma Aldrich
(Mumbai, India). Magnesium sulphate and anhy-
drous sodium chloride (heated at 650°C for 4 h
before use and kept in desiccator) were from
Merck India Ltd. (Mumbai, India) Primary sec-
ondary amine (PSA) and graphitized carbon black
(GCB) were purchased from M/s. Agilent
Technologies (Agilent Technologies India Pvt
Ltd, Chennai, India). Merck Millipore system
was used to collect ultra-pure water. Nylon filters
(0.2 µm) from PAL life sciences (PALL life
sciences, Bengaluru, India) were used to filter the
sample extracts.
Preparation of standard solutions
Stock solutions (1000 µg mL−1) of the five neoni-
cotinoid compounds were prepared individually
by dissolving the technical-grade material in acet-
onitrile (v/v) separately. These were labelled and
stored in a freezer at –20°C. From the stock solu-
tion, intermediate stock and working standard
solutions were prepared as mixes.
Sample preparation
The rice whole grain and rice straw samples were
collected from organic demo fields of Department
of Sustainable Organic Agriculture, Tamil Nadu
Agricultural University (TNAU), Coimbatore,
Tamil Nadu, India. Rice grains along with hull
(whole grains) were homogenized into fine pow-
der using blender. Rice straws were milled into
coarse powders using a Wiley mill at Department
of Forage and Fodder crops, TNAU and were used
after passing through 0.1 mm metal sieves.
Extraction and clean up
The QuEChERS method (Anastassiades et al.
2003) with following modifications was employed
for extraction and clean-up process. Homogenized
rice whole grain powder (10 g) was weighed out
into a 50-mL centrifuge tube. After adding 20 ml
of acetonitrile, the centrifuge tube was capped and
vortex shaken for 1 min. To this, 4 g anhydrous
magnesium sulphate and 1 g of sodium chloride
was added and again vortex shaken for 1 min to
mix the sample thoroughly. The samples were
centrifuged for 10 min at 6000 rpm. From this,
9 mL of supernatant was passed through 4 g of

anhydrous sodium sulphate to remove moisture
and out of this, 6 mL of extract was transferred
into centrifuge tube containing 100 mg PSA and
600 mg anhydrous magnesium sulphate. The sam-
ples were mixed thoroughly by vortexing for
1 min and centrifuged for 10 min at 3000 rpm.
Finally, 4 mL of acetonitrile layer was transferred
into a clean glass test tube and concentrated to
near dryness using nitrogen gas in a Turbovap
(Caliper life sciences, USA) at 40°C. The final
volume was reconstituted to 1 ml using acetoni-
trile and transferred into a 1.5 mL glass auto
sampler vial for LC/MS-MS analysis after filtering
through a 0.2 µm filter membrane.
For straw sample analysis, rice straw powder (2 g)
was taken into a 50 mL centrifuge tube. To the
sample, 5 mL distilled water was added and shaken
well to moisten the sample. This was followed by
addition of 20 mL of acetonitrile. The samples were
homogenized using silent crusher (Make: Heidolph,
Germany) for 5 min at 15,000 rpm. After adding 4 g
anhydrous magnesium sulphate and 1 g of sodium
chloride, the centrifuge tube was vortex-shaken for
1 min and centrifuged for 10 min at 6000 rpm. From
the supernatant, 9 ml was taken and dehydrated
using 4 g of anhydrous sodium sulphate, and again
6 ml of the extract was transferred into an 18-mL
centrifuge tube containing 10 mg GCB, 100 mg PSA
and 600 mg anhydrous magnesium sulphate. The
extract was mixed vigorously by vortexing for 1 min
and centrifuge-extracted for 10 min at 3000 rpm. An
aliquot of 4 mL of the supernatant was transferred to
Turbovap tube, dried under nitrogen gas and recon-
stituted to 1 mL with acetonitrile. This extract was
transferred into 1.5 mL glass auto sampler vial for
LC/MS-MS analysis after filtering through 0.2 µm
filter membrane.
Instrumentation
The chromatographic separation was carried out
in a Waters Alliance system using C18, 5 µm
Table 1. MRM ions and linearity of neonicotinoid anlaytes in LC-MS/MS.
Analyte Parent ion Quantifier ion Qualifier ion
Acetamiprid 223.160 126.115 56.222
Thiacloprid 253.096 126.126 90.230
Imidacloprid 256.132 209.146 175.205
Thiamethoxam 292.168 211.109 132.104
Clothianidin 250.104 169.108 132.106
FOOD ADDITIVES & CONTAMINANTS: PART A 3
(4.8 × 250 mm) column with a mobile phase of
acetonitrile: water acidified with 0.5% formic acid
(50:50, v/v) at 0.5 mL min−1 flow rate. With these
conditions, all the five analytes were detected in
10.0 min. Confirmation was done utilizing
Acquity (Waters, USA) Tandem Quadrupole
mass Detector (TQD) with Electrospray ionization
(ESI) interface. All the five analytes were ionized
in positive polarity. The standardized ESI condi-
tions were as follows: capillary voltage at 3.5 kV;
source block and desolvation temperatures were
150°C and 500°C, respectively, desolvation and
cone gas flows were fixed at 1100 and 50 L h−1,
respectively, and the collision gas flow was
0.18 mL min−1. Nitrogen was used for desolvation
purpose and also as cone gas, while the collision
gas was argon. Infusion was done at 20 μL min−1
and the lens voltages were standardized using
Tune Master (Mass Lynx software). For infusion
while tuning, working standards of 0.5 and
1.0 μg mL−1 were used. Multiple reaction moni-
toring mode was followed and the neonicotinoids
were detected as reported in Table 1.
Method validation
The efficacy of the developed method was proved
by assessment of specificity, linearity, limits of
detection and quantification, precision and accu-
racy. Organic rice samples with no residues were
used for all the analyses.
The linearity of neonicotinoids was studied
using five linear concentrations of the mix solu-
tion in the range of 0.025–0.25 μg mL−1. The
calibration standards were prepared using 100%
acetonitrile. Three replicates were made for each
concentration against which the detector’s
responses were plotted. Regression equation with
slope, y-intercept and coefficient of correlation
were evaluated for the five neonicotinoids. Matrix-
matched standards were also studied to prove that
there is no matrix effect. The LOD were calculated
Concentration range Calibration curve R2 value
0.025–0.25 188.883x + (−395.423) 0.9991
0.025–0.25 219.769x + (−389.492) 0.9995
0.025–0.25 42.4973x + (−152.17) 0.9974
0.025–0.25 18.127x + (−67.2196) 0.9961
0.025–0.25 35.6622x + (−63.6839) 0.9978
4 S. KARTHIKEYAN ET AL.

from the standard deviation associated with the

measurement of the pesticide taken during recov-
ery and students t value. For this purpose, seven
independent analyses of rice whole grain and rice
straw sample spiked with pesticides at a level of
0.025 mg kg−1 were performed. The one-sided
t-distribution was determined using the mean
value and standard deviation of replicate injec-
tions, and was multiplied with standard deviation.
For seven samples (with six degrees of freedom),
the t value for a 99% confidence interval is 3.14.
The limits of quantification (LOQs) were calcu-
lated by considering a value of 3.3 times the LOD.
In this present study, the recovery was tested
using a certified organic rice sample as
a reference matrix. The organic rice samples
were obtained from Department of Organic
farming, TNAU. Experiments were conducted
by spiking the reference matrix with neonico-
tinoid standard mix at five different concentra-
tions (0.025–0.25 mg kg−1) and replicated
seven times. Method precision was demon-
strated via intra-day variation studies and the
results were expressed as % RSD of the
measurement.
Farm gate sample analysis
In this study, 24 each of rice whole grain and rice
straw samples were collected from conventional
farmers field (20), IPM field (2) and organically
maintained fields (2) of Coimbatore region, Tamil
Nadu, India.
Results
Using LC-MS/MS, under ESI positive mode,
[M + H]+ parent ions were observed for all the
five analytes. No ions were observed under nega-
tive ESI mode. For each analyte, MRM transitions
were done for identification and quantitation in
a single run. The analytes were identified based on
the parent and two product ions (Figure 1).
Specificity was obtained with the standardized
chromatographic conditions set with the total run-
ning time of 10 min for all the five analytes tested.
Identification and quantification of the analytes at
a low concentration of 0.024 and 0.16 mg kg−1 in
the rice whole grain and rice straw matrix,
Figure 1. LC-MS/MS chromatogram of thiamethoxam standard
(0.025 mg kg−1).
respectively, was achieved with the tandem quad-
rupole mass detector coupled with
chromatography.
A linear equation for the calibration curve
was obtained for concentrations ranging from
0.025 to 0.252 μg mL−1. R2 value in the range
of 0.9961–0.9995 was obtained indicating
a good linearity and a precise linear relation
between the injected neonicotinoid mix in
acetonitrile and the corresponding peak area
(Table 1). Linear equation was also obtained
for matrix-matched standards of rice grain and
straw identical to calibration curve of standard
in acetonitrile and thus proved that there is no
matrix effect (Table 2) (Figures 2 and 3). The
retention times of the analytes in the extract
matched those of the calibration standard. The
detector response of individual analytes in
mixed calibration standards was not affected
by any of the other analytes in the mix solu-
tion. The LOD for rice whole grains ranged
from 0.007 to 0.0084 mg kg−1 and the LOQ
was in the range of 0.024–0.028 mg kg−1
(Table 3). LODs ranged from 0.005 to
0.15 mg kg−1 and LOQ ranged from 0.016 to
0.051 mg kg−1 for rice straw (Table 4).
The recoveries of neonicotinoids ranged from
74.9% to 115.7% and 60.0 to 104.8% for rice whole
 FOOD ADDITIVES & CONTAMINANTS: PART A 5

Table 2. Linearity of rice whole grain and rice straw matrix match neonicotinoid standards.
Rice grain Rice straw
Analyte Concentration range Calibration curve R2 value Calibration curve R2 value
Acetamiprid 0.025–0.25 189.156x + (−920.366) 0.981576 230.444x + 812.18 0.993600
Thiacloprid 0.025–0.25 415.58x + (−1646.3) 0.989100 397.135x + 1580.7 0.995023
Imidacloprid 0.025–0.25 34.8896x + (−146.474) 0.983934 39.2176x + 44.5258 0.991208
Thiamethoxam 0.025–0.25 34.5698x + (−115.568) 0.993438 30.393x + 20.035 0.984057
Clothianidin 0.025–0.25 10.9306x + (−40.2987) 0.978965 12.2628x + 129.183 0.982724

thiamethoxam residues (0.07 mg kg−1) (Figure 4)

above the FSSAI Maximum Residue Limit
(MRL) (0.02 mg kg−1) for polished rice, but
below the Japanese MRL for brown rice
(0.3 mg kg−1) (Table 5). No MRL is available for
paddy grains with hull (rice whole grain). Residues
were not detected in any of the rice straw sample
tested.

Figure 2. LC-MS/MS chromatogram of thiamethoxam for rice
whole grain matrix-matched standard (0.025 mg kg−1).
Figure 3. LC-MS/MS chromatogram of thiamethoxam for rice
straw matrix-matched standard (0.025 mg kg−1).
grains and rice straw, respectively (Tables 3 and
4). The intraday precision observed in terms of
RSD ranged between 3.35% and 17.55%, and
2.19% and 10.31% for grain and straw,
respectively.
Monitoring of farm gate samples comprising
conventional field, IPM and organic fields samples
of two crop seasons by the validated method
revealed that one sample of rice whole grain, out
of 24 samples, was contaminated with
Discussion
In the present study, a modified QuEChERS sam-
ple preparation procedure for LC-MS/MS analysis
was validated to determine neonicotinoid residue
in rice whole grain and rice straw. Studies shown
reported that in plant samples of cereals such as
rice, wheat and oats, the organic contents that are
co-extracted along with the residues act as inter-
ferences in the chromatograms (Schwedler et al.
2000; Koesukwiwat et al. 2010). However, in this
study, interferences were overcome by improved
clean up step. The samples were extracted using
acetonitrile and the dispersive solid-phase clean-
up procedure was followed effectively to remove
the interfering co-extractives from grain and straw
samples. In case of rice straw, while coloured
extract was obtained due to the chlorophyll con-
tent, this was removed by using GCB in the clean-
up step. Recovery above 70% and RSD below 20%
were obtained for rice whole grains. In case of rice
straw, the recovery at/above the level of 60% at
few concentrations may be due to interference by
organic matters but acceptable as the RSD was less
than 20%. The results indicate that the present
method has a good recovery rate within the cri-
teria set by SANTE (2017) for both rice whole
grain and rice straw.
MRLs for neonicotinoid pesticides are not set
for rice whole grains (with hull) and rice straw
under Food Safety and Standards Authority of
6 S. KARTHIKEYAN ET AL.

Table 3. Recovery, LOD and LOQ of neonicotinoid insecticide residues in paddy grains.
Spiked level (mg kg−1)
0.025 0.063 0.125 0.187 0.25
LOD LOQ
Pesticides Recovery (%) RSD Recovery (%) RSD Recovery (%) RSD Recovery (%) RSD Recovery (%) RSD (mg kg−1) (mg kg−1)
Acetamiprid 76.10 12.30 91.76 6.81 96.84 15.01 103.99 8.18 110.18 5.65 0.007 0.024
Thiacloprid 88.67 12.13 90.78 6.47 107.94 17.55 115.70 8.87 100.01 6.66 0.0084 0.028
Imidacloprid 74.92 12.67 90.68 8.00 96.59 16.11 104.19 11.37 91.05 6.26 0.008 0.025
Thiamethoxam 80.68 12.92 91.43 7.70 96.56 11.84 111.18 10.21 87.29 4.56 0.008 0.027
Clothianidin 87.75 10.76 89.49 6.22 92.63 10.41 100.96 8.44 79.01 3.35 0.007 0.024

Table 4. Recovery, LOD and LOQ of neonicotinoid insecticide residues in paddy straw.
Spiked level (mg kg−1)
0.025 0.063 0.125 0.187 0.25
LOD LOQ
Pesticides Recovery (%) RSD Recovery (%) RSD Recovery (%) RSD Recovery (%) RSD Recovery (%) RSD (mg kg−1) (mg kg−1)
Acetamiprid 82.09 9.60 68.86 2.19 68.77 4.22 75.51 9.50 74.71 2.74 0.006 0.021
Thiacloprid 80.50 7.68 68.46 3.28 69.84 3.83 77.71 7.61 75.50 3.71 0.005 0.016
Imidacloprid 104.81 7.94 73.94 3.95 71.95 10.31 85.15 9.86 74.56 3.70 0.015 0.050
Thiamethoxam 84.09 8.14 70.29 6.23 69.42 10.05 78.81 10.25 74.42 6.18 0.01 0.038
Clothianidin 80.58 4.58 60.00 7.65 60.01 6.81 69.41 4.56 62.55 3.37 0.009 0.031

Table 5. MRL values for neonicotinoids in rice.

Rice grain (mg kg−1)
Analyte EU MRL Japanese MRL for brown rice FSSAI
Acetamiprid 0.01 – –
Thiacloprid 0.02 0.1 0.01
Imidacloprid 1.5 1 0.05
Thiamethoxam 0.01 0.3 0.02
Clothianidin 0.5 1 0.02

sample. Thiamethoxam residues may be removed

Figure 4. LC-MS/MS chromatogram of paddy grain sample
detected with thiamethoxam residues.
India and Codex Alimentarius Commission.
However, MRLs available for polished rice and
brown rice are listed for the comparison of results
(Table 5). But this study has opened the need for
establishing MRLs for rice whole grains, bran and
straw, as they are used as important feed and
fodder.
Monitoring of farm gate samples revealed the
presence of thiamethoxam in one rice whole grain
when grains are dehulled and processed, but this
may be carried to bran while processing the
grains. Teló et al. (2015) also detected residues of
thiamethoxam in rice hull, bran and polished rice
grains, and the residues were found to be more in
hull and rice bran. Residues were not detected in
straw samples. Studies on the fate of neonicoti-
noids after absorption into the plant system are
meagre. This study is the first attempt to under-
stand the neonicotinoid residues in rice straw.
Neonicotinoids are said to be highly persistent in
soil (Goulson 2013). Since neonicotinoids are sys-
temic in nature, they are absorbed by the crop in
all the modes of delivery to the crop system (seed
treatment, foliar application and soil drenching)
(Simon-Delso et al. 2015). Because of the disre-
gard of post-harvest intervals by the farmer, the
thiamethoxam residues absorbed inside the plant
might be detected in the grains. But the rice straw

samples after harvest were sun-dried before sto-
rage. This practice might have caused the residues
to dissipate to below detectable levels in straw. In
many South East Asian countries, rice whole
grains and rice straw are used for multiple pur-
poses, mainly as food, feed and fodder. With an
ever-increasing scale of use of neonicotinoids, it
becomes necessary to monitor its residues in rice
whole grains and rice straw in the interest of safety
to consumers and livestock.
Conclusion
The result of validation parameters demonstrates
that the usage of LC-MS/MS in detecting neoni-
cotinoid residue in rice whole grains and rice
straw samples is acceptable because of the lower
LOQ level, high recovery and precision and
applicable to monitor neonicotinoid residues.
Many studies have concentrated on residues in
finished grains like rice. But the present study
focused on the whole grains with hull and straw
which are important feed and fodders for livestock
and other vertebrates like birds, apart from being
a food commodity.
Acknowledgments
The authors would like to thank National Institute of Plant
Health Management, Hyderabad, India for financial support
of this study and the Director, Centre for Plant Protection
Studies, TNAU for providing facilities at Pesticide
Toxicology Laboratory, TNAU.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by National Institute of Plant
Health Management, Hyderabad, India under grant
NIPHM/CPPS/CBE/AEN/2016/R010.
Ethical approval
This article does not contain any studies with human parti-
cipants or animals performed by any of the authors.
FOOD ADDITIVES & CONTAMINANTS: PART A 7
ORCID
S. Karthikeyan http://orcid.org/0000-0001-7725-5464
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