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  <front>
    <journal-meta />
    <article-meta>
      <title-group>
        <article-title>Dissipation Dynamic of Insecticide Chlorantraniliprole in Pear Fruits</article-title>
      </title-group>
      <contrib-group>
        <contrib contrib-type="author">
          <string-name>Sanja Lazić</string-name>
          <email>sanja.lazic@polj.edu.rs</email>
          <xref ref-type="aff" rid="aff0">0</xref>
        </contrib>
        <contrib contrib-type="author">
          <string-name>Dragana Šunjka</string-name>
          <email>dragana.sunjka@polj.edu.rs</email>
          <xref ref-type="aff" rid="aff0">0</xref>
        </contrib>
        <contrib contrib-type="author">
          <string-name>Slavica Vuković</string-name>
          <xref ref-type="aff" rid="aff0">0</xref>
        </contrib>
        <contrib contrib-type="author">
          <string-name>Antonije Žunić</string-name>
          <email>antonije.zunic@polj.uns.ac.rs</email>
          <xref ref-type="aff" rid="aff0">0</xref>
        </contrib>
        <aff id="aff0">
          <label>0</label>
          <institution>University of Novi Sad, Faculty of Agriculture</institution>
          ,
          <addr-line>Trg Dositeja Obradovića 8, Novi Sad</addr-line>
          ,
          <country>Republic of Serbia</country>
        </aff>
      </contrib-group>
      <pub-date>
        <year>2021</year>
      </pub-date>
      <fpage>488</fpage>
      <lpage>491</lpage>
      <abstract>
        <p>This study was conducted in order to evaluate the dissipation dynamic of insecticide chlorantraniliprole in pear fruits. Plant protection product (PPP) based on chlorantraniliprole was applied at the recommended rate, for the control of the main pear pest, Cacopsylla pyri. For the analysis of insecticide residues, the QuEChERS-based method, followed by HPLC analysis was validated in accordance with SANTE/12682/2019. In this study, the maximum level of the residues in the pear fruits (4.95 mg/kg) was obtained 1h after the application of PPP, i.e., after drying the deposit. After 14 days, the level of chlorantraniliprole was 0.16 mg/kg, which is significantly below the MRL of 0.5 mg/kg. The results indicated that chlorantraniliprole exhibited first-order kinetics dissipation, with a half-life of 2.76 days. Pear, chlorantraniliprole, dissipation dynamic, half-life Chlorantraniliprole [3-bromo-N-[4-chloro-2-methyl-6-[(methyl amino) carbonyl] phenyl]-1-(3chloro-2-pyridinyl)-1H-pyrazole-5-caroxamide] is an anthranilic diamide insecticide. This substance acts on insect ryanodine receptors, playing a critical role in muscle function. Due to its specific structure, it shows remarkable selectivity and safety for mammals [1]. Insecticides based on chlorantraniliprole are used for the control of the most important apple, peach, pear, grape, cabbage, tomato, and potato pests.</p>
      </abstract>
    </article-meta>
  </front>
  <body>
    <sec id="sec-1">
      <title>1. Introduction</title>
      <p>2.1.
conducted
according to the standard</p>
      <p>EPPO
methods. Plant protection
product based on</p>
      <p>2022 Copyright for this paper by its authors.
chlorantraniliprole (45 g a. i./l, SC) was foliar applied at the concentration of 0.1%, with water
consumption of 1000 l/ha. The treatment was conducted in order to control the presence of Cacopsylla
pyri in the pear fruits (BBCH 74). The experiment was set up in four replications, as a randomized
block system.</p>
      <p>
        To investigate the dissipation dynamics and terminal residue of insecticides, pear fruits were
randomly collected at 0 (1 h), 2, 4, 6, 8, 10, 12, and 14 d after the application of chlorantraniliprole,
according to the FAO/WHO recommendations [
        <xref ref-type="bibr" rid="ref4">4</xref>
        ]. Fresh samples (approx. 500 g) were transferred to
the laboratory within 2 h after collection, homogenized and stored at −20 °C before analysis.
2.2.
      </p>
    </sec>
    <sec id="sec-2">
      <title>Extraction and Analysis of Insecticide Residues</title>
      <p>
        The content of insecticide residues in the analyzed pear samples was assayed following a
QuEChERS procedure [
        <xref ref-type="bibr" rid="ref5">5</xref>
        ]. The procedure involved the extraction of 10 g pear fruits with 10 ml
acetonitrile. Subsequently, a liquid-liquid partition was performed by adding a mixture of MgSO4,
NaCl, trisodium citrate dihydrate, and disodium hydrogen citrate sesquihydrate. After vortex and
centrifugation, 6 ml of the aliquot was added into a tube containing 150 mg primary secondary amine
(PSA) sorbent and 0.9 g anhydrous MgSO4, as a cleanup step. After the shaking and centrifugation, the
extract was evaporated till dry and dissolved in 1 ml of acetonitrile and analyzed.
      </p>
      <p>Detection and quantification were performed with an Agilent 1100 HPLC system (USA), equipped
with a photodiode array detector. In terms of chromatographic conditions, a column Zorbax XDE
(50 mm × 4.6 mm, 5 μm film thickness) was used. The method was validated through linearity,
precision, the limit of detection and quantification (LOD, LOQ), matrix effect, and accuracy.</p>
    </sec>
    <sec id="sec-3">
      <title>3. Results and Discussion</title>
      <p>
        The results obtained for the validation parameters are shown in Table 1. The analytical methods
have been validated according to SANTE/12682/2019 standard [
        <xref ref-type="bibr" rid="ref6">6</xref>
        ].
      </p>
      <p>After the application of chlorantraniliprole-based insecticide, the maximum level of the residues in
the pear fruits (4.95 mg/kg) was obtained after 1 h, i.e. after drying the deposit (Table 2). In the samples
collected two days after the treatment, the average value of chlorantraniliprole residues was 3.29 mg/kg,
with a loss of 33.54%.</p>
      <p>
        In the next days, chlorantraniliprole content in pear fruits decreased, and at the end of the pre-harvest
interval, it was 0.16 mg/kg. In this study, chlorantraniliprole residues were at the MRL level of 0.5
mg/kg eight days after the application. The dissipation rate of chlorantraniliprole in pear fruits followed
the first-order kinetic equation (1) was used [
        <xref ref-type="bibr" rid="ref7">7</xref>
        ]:
where Ct is the residual pesticide concentration (mg/kg) at time t (days) after application; C0 is the
initial pesticide concentration, and k is the pesticide dissipation rate constant. The half-life (t1/2) was
calculated from the equation:
      </p>
      <p>Ct=C0×exp(−k×t)
t1/2=ln(2)/k
(1)
(2)</p>
      <p>In order to describe the dissipation rate of pesticide's active ingredient in crops, first-order kinetics
has been extensively used. In this study, the results showed a gradual decrease of chlorantraniliprole in
pear fruits, with a correlation coefficient of 0.988 (Table 3). The half-life of chlorantraniliprole in pear
fruits, based on the obtained results, was 0.6 days.</p>
      <p>
        According to the available literature, a number of studies dealt with the behavior of
chlorantraniliprole in plants [
        <xref ref-type="bibr" rid="ref8 ref9">8, 9</xref>
        ]. The half-life of chlorantrilantriliprole in cauliflower was 1.36 days
[
        <xref ref-type="bibr" rid="ref10">10</xref>
        ], while in grapes was 2.70 days [
        <xref ref-type="bibr" rid="ref2">2</xref>
        ]. In our previous research, the dissipation dynamic of
chlorantraniliprole in peach fruits showed a t1/2 of 3.15 days [
        <xref ref-type="bibr" rid="ref3">3</xref>
        ]. However, this the first study conducted
in peach fruits.
      </p>
    </sec>
    <sec id="sec-4">
      <title>4. Conclusions</title>
      <p>In this study, a simple and reliable method for the determination of residues of insecticide
chlorantraniliprole in pear fruit was validated. Furthermore, the dissipation dynamic was also studied.
The obtained results indicated that chlorantraniliprole degrades rapidly in pear fruits. After the
application of chlorantraniliprole-based insecticide for the control of the main pear pest, the half-life
was 2.76 days. Obtained results could be useful for the safe use of chlorantraniliprole insecticide in pest
management of pear.</p>
    </sec>
    <sec id="sec-5">
      <title>5. Acknowledgements</title>
      <p>This study is a part of the project No. 451-03-68/2022-14/200117, funded by the Ministry of
Education, Science and Technological Development of the Republic of Serbia.</p>
    </sec>
    <sec id="sec-6">
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    </sec>
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