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Development of a New Magnetic Dispersive Solid-Phase Microextraction Coupled with GC-MS for the Determination of Five Organophosphorus Pesticides from Vegetable Samples

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Abstract

A magnetic dispersive solid-phase microextraction procedure (MDμ-SPE) was developed to extract organophosphorus pesticides (OPP), including ethion, chlorpyrifos, diazinon, malathion, and fenitrothion, from vegetable samples before their analysis with gas chromatography/mass spectroscopy (GC/MS). Magnetic graphene@Fe3O4@SiO2@TiO2 nanocomposites were synthesized as a unique sorbent using the sol-gel and co-precipitation procedures. The ability of the prepared sorbent to extract the analytes was compared with several other sorbents. Effective factors in the MDμ-SPE method were thoroughly optimized by one factor at a time and the experimental design approach. Under the optimum condition of the OPP determination, the calibration curves were linear over a wide range of analyte concentrations with the correlation coefficient (R2) between 0.995 and 0.9986. Besides, the method showed high preconcentration factors (PF ≥ 217) and suitable relative standard deviations (RSD ≤ 4.73). Limit of detections (LODs) and limit of quantitations (LOQs) were in the range of 0.06-1.49 and 0.2-4.96 ng mL−1 for water sample analysis, respectively. Application of the method for the determination of the analytes in real samples such as tomato and lettuce samples indicated the method is proper for the OPP measurement in the vegetable samples with a recovery percentage between 93.89 and 106.67% and a relative standard deviation of less than 5.77%. The procedure for the residue determination of organophosphorus pesticides has various advantages such as no need for centrifugation step to the sorbent separation, low sorbent and sample solution consumption, high sensitivity, and low analysis time.

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References

  • Amiri A (2016) Solid-phase microextraction-based sol–gel technique. TrAC Trends Anal Chem 75:57–74

    CAS  Google Scholar 

  • Arunan E, Desiraju GR, Klein RA, Sadlej J, Scheiner S, Alkorta I, Clary DC, Crabtree RH, Dannenberg JJ, Hobza P (2011) Definition of the hydrogen bond (IUPAC Recommendations 2011). Pure Appl Chem 83:1637–1641

    CAS  Google Scholar 

  • Ayazi Z (2017) Application of nanocomposite-based sorbents in microextraction techniques: a review. Analyst 142:721–739

    CAS  PubMed  Google Scholar 

  • Bagheri H, Piri-Moghadam H, Naderi M (2012) Towards greater mechanical, thermal and chemical stability in solid-phase microextraction. TrAC Trends Anal Chem 34:126–139

    CAS  Google Scholar 

  • Cheng H, Song Y, Bian Y, Wang F, Ji R, He W, Gu C, Ouyang G, Jiang X (2018) A nanoporous carbon material coated onto steel wires for solid-phase microextraction of chlorobenzenes prior to their quantitation by gas chromatography. Microchim Acta 185:56

    Google Scholar 

  • Derbalah A, Chidya R, Jadoon W, Sakugawa H (2019) Temporal trends in organophosphorus pesticides use and concentrations in river water in Japan, and risk assessment. J Environ Sci 79:135–152

    Google Scholar 

  • dos Anjos JP, de Andrade JB (2015) Simultaneous determination of pesticide multiresidues in white wine and rosé wine by SDME/GC-MS. Microchem J 120:69–76

    Google Scholar 

  • Fukuto TR (1990) Mechanism of action of organophosphorus and carbamate insecticides. Environ Health Perspect 87:245–254

    CAS  PubMed  PubMed Central  Google Scholar 

  • Ghorbani M, Chamsaz M, Rounaghi GH (2016) Glycine functionalized multiwall carbon nanotubes as a novel hollow fiber solid-phase microextraction sorbent for pre-concentration of venlafaxine and o-desmethylvenlafaxine in biological and water samples prior to determination by high-performance liquid chromatography. Anal Bioanal Chem 408:4247–4256

    CAS  PubMed  Google Scholar 

  • Ghorbani M, Aghamohammadhassan M, Chamsaz M, Akhlaghi H, Pedramrad T (2019) Dispersive solid phase microextraction. TrAC Trends Anal Chem 118:793–809

    CAS  Google Scholar 

  • Ghorbani M, Aghamohammadhassan M, Ghorbani H, Zabihi A (2020) Trends in sorbent development for dispersive micro-solid phase extraction. Microchem J 158:105250

    CAS  Google Scholar 

  • Guo J, Park S-J, Meng L-Y, Jin X (2017) Applications of carbon-based materials in solid phase microextraction: a review. Carbon Lett (Carbon Lett) 24:10–17

    Google Scholar 

  • Hadjmohammadi MR, Fatemi MH, Shakeri P (2012) Developing an alcoholic-assisted dispersive liquid–liquid microextraction for extraction of pentachlorophenol in water. J Sep Sci 35:3375–3380

    CAS  PubMed  Google Scholar 

  • Hamidi S, Alipour-Ghorbani N, Hamidi A (2018) Solid phase microextraction techniques in determination of biomarkers. Crit Rev Anal Chem 48:239–251

    CAS  PubMed  Google Scholar 

  • Hooshmand S, Es’ haghi Z (2018) Hydrophilic modified magnetic multi-walled carbon nanotube for dispersive solid/liquid phase microextraction of sunitinib in human samples. Anal Biochem 542:76–83

    CAS  PubMed  Google Scholar 

  • Ismailzadeh A, Masrournia M, Es’haghi Z, Bozorgmehr MR (2020) An environmentally friendly sample pre-treatment method based on magnetic ionic liquids for trace determination of nitrotoluene compounds in soil and water samples by gas chromatography–mass spectrometry using response surface methodology. Chem Pap 74:2929–2943

    CAS  Google Scholar 

  • Karimi-Maleh H, Cellat K, Arıkan K, Savk A, Karimi F, Şen F (2020a) Palladium–nickel nanoparticles decorated on functionalized-MWCNT for high precision non-enzymatic glucose sensing. Mater Chem Phys. https://doi.org/10.1016/j.matchemphys.2020.123042

  • Karimi-Maleh H, Karimi F, Malekmohammadi S, Zakariae N, Esmaeili R, Rostamnia S, Yola ML, Atar N, Movagharnezhad S, Rajendran S (2020b) An amplified voltammetric sensor based on platinum nanoparticle/polyoxometalate/two-dimensional hexagonal boron nitride nanosheets composite and ionic liquid for determination of N-hydroxysuccinimide in water samples. J Mol Liq 310:113185. https://doi.org/10.1016/j.molliq.2020.113185

  • Karimi-Maleh H, Kumar BG, Rajendran S, Qin J, Vadivel S, Durgalakshmi D, Gracia F, Soto-Moscoso M, Orooji Y, Karimi F (2020c) Tuning of metal oxides photocatalytic performance using Ag nanoparticles integration. J Mol Liq 314:113588

    CAS  Google Scholar 

  • Karimi-Maleh H, Shafieizadeh M, Taher MA, Opoku F, Kiarii EM, Govender PP, Ranjbari S, Rezapour M, Orooji Y (2020d) The role of magnetite/graphene oxide nano-composite as a high-efficiency adsorbent for removal of phenazopyridine residues from water samples, an experimental/theoretical investigation. J Mol Liq 298:112040

    CAS  Google Scholar 

  • Kaykhaii M, Mirmoghaddam M, Yahyavi H (2017) Applications of graphene-based materials in chromatography and sample preparation: a review. Curr Chromatogr 4:4–33

    CAS  Google Scholar 

  • Kermani M, Jafari MT, Saraji M (2019) Porous magnetized carbon sheet nanocomposites for dispersive solid-phase microextraction of organophosphorus pesticides prior to analysis by gas chromatography-ion mobility spectrometry. Microchim Acta 186:88

    Google Scholar 

  • Khodadadi A, Faghih-Mirzaei E, Karimi-Maleh H, Abbaspourrad A, Agarwal S, Gupta VK (2019) A new epirubicin biosensor based on amplifying DNA interactions with polypyrrole and nitrogen-doped reduced graphene: experimental and docking theoretical investigations. Sensors Actuators B Chem 284:568–574

    CAS  Google Scholar 

  • Kim K-H, Kabir E, Jahan SA (2017) Exposure to pesticides and the associated human health effects. Sci Total Environ 575:525–535

    CAS  PubMed  Google Scholar 

  • Li N, Jiang H-L, Wang X, Wang X, Xu G, Zhang B, Wang L, Zhao R-S, Lin J-M (2018) Recent advances in graphene-based magnetic composites for magnetic solid-phase extraction. TrAC Trends Anal Chem 102:60–74

    CAS  Google Scholar 

  • Lim JY, Mubarak N, Abdullah E, Nizamuddin S, Khalid M (2018) Recent trends in the synthesis of graphene and graphene oxide based nanomaterials for removal of heavy metals—a review. J Ind Eng Chem 66:29–44

    CAS  Google Scholar 

  • Liu H, Kong W, Qi Y, Gong B, Miao Q, Wei J, Yang M (2014) Streamlined pretreatment and GC–FPD analysis of multi-pesticide residues in perennial Morinda roots: a tropical or subtropical plant. Chemosphere 95:33–40

    CAS  PubMed  Google Scholar 

  • Liu C, Li Y, Duan Q (2020) Preparation of magnetic and thermal dual-responsive zinc-tetracarboxyl-phthalocyanine-g-Fe3O4@ SiO2@ TiO2-g-poly (N-isopropyl acrylamide) core-shell green photocatalyst. Appl Surf Sci 503:144111

    CAS  Google Scholar 

  • López-García I, Marín-Hernández JJ, Hernández-Córdoba M (2018) Microcrystalline cellulose for the dispersive solid-phase microextraction and sensitive determination of chromium in water using electrothermal atomic absorption spectrometry. J Anal At Spectrom 33:1529–1535

    Google Scholar 

  • Łozowicka B (2013) The development, validation and application of a GC-dual detector (NPD-ECD) multi-pesticide residue method for monitoring bee poisoning incidents. Ecotoxicol Environ Saf 97:210–222

    PubMed  Google Scholar 

  • Maya F, Ghani M (2019) Ordered macro/micro-porous metal-organic framework of type ZIF-8 in a steel fiber as a sorbent for solid-phase microextraction of BTEX. Microchim Acta 186:425

    Google Scholar 

  • Mohanraj J, Durgalakshmi D, Rakkesh RA, Balakumar S, Rajendran S, Karimi-Maleh H (2020) Facile synthesis of paper based graphene electrodes for point of care devices: a double stranded DNA (dsDNA) biosensor. J Colloid Interface Sci 566:463–472

    CAS  PubMed  Google Scholar 

  • Mondal P, Anweshan A, Purkait MK (2020) Green synthesis and environmental application of Iron-based nanomaterials and nanocomposite: a review. Chemosphere 259:127509. https://doi.org/10.1016/j.chemosphere.2020.127509

    Article  CAS  PubMed  Google Scholar 

  • Naksen W, Prapamontol T, Mangklabruks A, Chantara S, Thavornyutikarn P, Robson MG, Ryan PB, Barr DB, Panuwet P (2016) A single method for detecting 11 organophosphate pesticides in human plasma and breastmilk using GC-FPD. J Chromatogr B 1025:92–104

    CAS  Google Scholar 

  • Nasrollahpour A, Moradi S, Baniamerian M (2017) Vortex-assisted dispersive solid-phase microextraction using ionic liquid-modified metal-organic frameworks of PAHs from environmental water, vegetable, and fruit juice samples. Food Anal Methods 10:2815–2826

    Google Scholar 

  • Nazari N, Masrournia M, Es’ haghi Z, Bozorgmehr M (2016) Simultaneous extraction and preconcentration of aniline, phenol, and naphthalene using magnetite–graphene oxide composites before gas chromatography determination. J Sep Sci 3:3046–3053

    Google Scholar 

  • Ouyang G, Jiang R (2016) Solid phase microextraction: recent developments and applications. Springer

  • Piri-Moghadam H, Ahmadi F, Pawliszyn J (2016) A critical review of solid phase microextraction for analysis of water samples. TrAC Trends Anal Chem 85:133–143

    CAS  Google Scholar 

  • Sapbamrer R, Hongsibsong S (2014) Organophosphorus pesticide residues in vegetables from farms, markets, and a supermarket around Kwan Phayao Lake of Northern Thailand. Arch Environ Contam Toxicol 67:60–67

    CAS  PubMed  Google Scholar 

  • Shirgholami MA, Mirjalili M, Nasirizadeh N (2017) Preparation of A MWCNT-graphite composite based on sol gel method for dye removal. Orient J Chem 33:676–685

    CAS  Google Scholar 

  • Sodeifian G, Ardestani NS, Sajadian SA (2019) Extraction of seed oil from Diospyros lotus optimized using response surface methodology. J For Res 30:709–719

    CAS  Google Scholar 

  • Souza-Silva ÉA, Gionfriddo E, Pawliszyn J (2015) A critical review of the state of the art of solid-phase microextraction of complex matrices II. Food analysis. TrAC Trends Anal Chem 71:236–248

    CAS  Google Scholar 

  • Sun P, Yu F, Lu J, Zhang M, Wang H, Xu D, Lu L (2019) In vivo effects of neomycin sulfate on non-specific immunity, oxidative damage and replication of cyprinid herpesvirus 2 in crucian carp (Carassius auratus gibelio). Aquac Fish 4:67–73

    Google Scholar 

  • Tahernejad-Javazmi F, Shabani-Nooshabadi M, Karimi-Maleh H (2019) 3D reduced graphene oxide/FeNi3-ionic liquid nanocomposite modified sensor; an electrical synergic effect for development of tert-butylhydroquinone and folic acid sensor. Compos Part B 172:666–670

    CAS  Google Scholar 

  • Tian F, Liu W, Fang H, An M, Duan S (2014) Determination of six organophosphorus pesticides in water by single-drop microextraction coupled with GC-NPD. Chromatographia 77:487–492

    CAS  Google Scholar 

  • Tsai W-H, Huang T-C, Huang J-J, Hsue Y-H, Chuang H-Y (2009) Dispersive solid-phase microextraction method for sample extraction in the analysis of four tetracyclines in water and milk samples by high-performance liquid chromatography with diode-array detection. J Chromatogr A 1216:2263–2269

    CAS  PubMed  Google Scholar 

  • Vale A (2015) Organophosphorus insecticide poisoning. BMJ Clin Evid 2015:2102

    PubMed  PubMed Central  Google Scholar 

  • Wang P, Luo M, Liu D, Zhan J, Liu X, Wang F, Zhou Z (2018) Application of a magnetic graphene nanocomposite for organophosphorus pesticide extraction in environmental water samples. J Chromatogr A 1535:9–16

    CAS  PubMed  Google Scholar 

  • Weinhold F, Klein RA (2014) What is a hydrogen bond? Resonance covalency in the supramolecular domain. Chem Educ Res Pract 15:276–285

    CAS  Google Scholar 

  • Yu X, Liu S, Yu J (2011) Superparamagnetic γ-Fe2O3@ SiO2@ TiO2 composite microspheres with superior photocatalytic properties. Appl Catal B Environ 104:12–20

    CAS  Google Scholar 

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Acknowledgments

The authors are grateful to the Islamic Azad University of Mashhad, Iran, for its support.

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Correspondence to Mahboubeh Masrournia.

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Shahram Vaziri Dozein declares that he has no conflict of interest. Mahboubeh Masrournia declares that he has no conflict of interest. Zarrin Es’haghi declares that he has no conflict of interest. Mohammad Reza Bozorgmehr declares that he has no conflict of interest.

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Dozein, S.V., Masrournia, M., Es’haghi, Z. et al. Development of a New Magnetic Dispersive Solid-Phase Microextraction Coupled with GC-MS for the Determination of Five Organophosphorus Pesticides from Vegetable Samples. Food Anal. Methods 14, 674–686 (2021). https://doi.org/10.1007/s12161-020-01906-0

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