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Magnetite-sporopollenin/graphene oxide as new preconcentration adsorbent for removal of polar organophosphorus pesticides in vegetables

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Abstract

In this study, a new magnetic adsorbent based on magnetite-sporopollenin/graphene oxide (Fe3O4-SP/GO) was successfully developed. The adsorbent was applied for magnetic solid phase extraction (MSPE) of three selected polar organophosphorus pesticides (OPPs), namely, dimethoate, phenthoate, and phosphamidon, prior to gas chromatography analysis with electron capture detection (GC-μECD). The Fe3O4-SP/GO adsorbent combines the advantages of superior adsorption capability of the modified sporopollenin (SP) with graphene oxide (GO) and magnetite (Fe3O4) for easy isolation from sample solution. Several MSPE parameters were optimized. Under optimized conditions, excellent linearity (R2 ≥ 0.9994) was achieved using matrix match calibration in the range of 0.1 to 500 ng mL−1. The limit of detection (LOD) method (S/N = 3) was from 0.02 to 0.05 ng mL−1. The developed Fe3O4-SP/GO MSPE method was successfully applied for the determination of these three polar OPPs in cucumber, long beans, bell pepper, and tomato samples. Good recoveries (81.0–120.0%) and good relative standard deviation (RSD) (1.4–7.8%, n = 3) were obtained for the spiked OPPs (1 ng mL−1) from real samples. This study is beneficial for adsorptive removal of toxic pesticide compounds from vegetable samples.

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References

  1. Ali AA, Sara K, Homeira E, Nafiseh S, Niloofar J (2015) Polypyrrole/magnetic nanoparticles composite as an efficient sorbent for dispersive micro solid phase extraction of antidepressant drugs from biological fluids. Int J Pharm 494:102–112

  2. Barakat MA (2011) New trends in removing heavy metals from industrial wastewater. Arab J Chem 4:361–367

  3. Benelli G (2018a) Mode of action of nanoparticles against insects. Environ Sci Pollut Res 25(13):12329–12341

  4. Benelli G (2018b) Plant-borne compounds and nanoparticles: challenges for medicine, parasitology and entomology. Environ Sci Pollut Res 25(11):10149–10150

  5. Benelli G, Pavela R, Petrelli R, Cappellacci L, Santini G, Fiorini D, Sut S, Dall’Acqua S, Canale A, Maggi F (2018) The essential oil from industrial hemp (Cannabis sativa L.) by-products as an effective tool for insect pest management in organic crops. Ind Crop Prod 122:308–315

  6. Bianchi F, Chiesi V, Casoli F, Luches P, Nasi L, Careri M, Mangia A (2012) Magnetic solid phase extraction based on diphenyl functionalization of Fe3O4 magnetic nanoparticles for the determination of polycyclic aromatic hydrocarbons in urine samples. J Chromatogr A 1231:8–15

  7. Bidari A, Ganjali MR, Norouzi P, Hosseini MRM, Assadi Y (2011) Sample preparation method for the analysis of some organophosphorus pesticides residues in tomato by ultrasound-assisted solvent extraction followed by dispersive liquid–liquid microextraction. Food Chem 126:1840–1844

  8. EPA (2003) Guidelines establishing test procedures for the analysis of pollutants; analytical methods for biological pollutants in ambient water; final rule. US EPA federal method registry 40 CFR part 136

  9. Fenik J, Tankiewicz M, Biziuk M (2011) Properties and determination of pesticides in fruits and vegetables. TrAC Trends Anal Chem 30:814–826

  10. Guan W, Wang Y, Xu F, Guan Y (2008) Poly(phthalazine ether sulfoneketone) as novel stationary phase for stir bar sorptive extraction of organochlorine compounds and organophosphorus pesticides. J Chromatogr A 1177(1):28–35

  11. Guan H, Brewer EW, Garris ST, Morgan SL (2010) Disposable pipette extraction for the analysis of pesticides in fruits and vegetables using gas chromatography/mass spectrometry. J Chromatogr A 1217(12):1867–1874

  12. Gubbuk IH (2011) Isotherms and thermodynamics for the sorption of heavy metal ions onto functionalized sporopollenin. J Hazard Mater 186:416–422

  13. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339–1339

  14. Igarashi, Yotsuyanagi (1992) Homogeneous liquid-liquid extraction by pH dependent phase separation with a fluorocarbon ionic surfactant and its application to the preconcentration of porphyrin compounds. Microchim Acta 106(1–2):37–44

  15. Jabbari M, Razmi H, Farrokhzadeh S (2016) Application of magnetic graphene nanoparticles for determination of organophosphorus pesticides using solid phase microextraction. Chromatographia 79(15–16):985–993

  16. Jiang L, Huang T, Feng S, Wang J (2016) Zirconium(IV) functionalized magnetic nanocomposites for extraction of organophosphorus pesticides from environmental water samples. J Chromatogr A 1456:49–57

  17. Kamboh MA, Wan Ibrahim WA, Rashidi Nodeh H, Sanagi MM, Sherazi STH (2016) The removal of organophosphorus pesticides from water using a new amino-substituted calixarene based magnetic sporopollenin. New J Chem 40(4):3130–3138

  18. Li Z, Bai S, Hou M, Wang C, Wang Z (2012) Magnetic graphene nanoparticles for the preconcentration of chloroacetanilide herbicides from water samples prior to determination by GC-ECD. Anal Lett 46:1012–1024

  19. Li X, Liu Xu L, Wen Y, Ma J, Wu Z (2015) Highly dispersed Pd/PdO/Fe2O3 nanoparticles in SBA-15: for fenton-like process: confinement and synergistic effects. Appl Catal B Environ 165:79–86

  20. Lucchi A, Benelli G (2018) Towards pesticide-free farming? Sharing needs and knowledge promotes integrated pest management. Environ Sci Pollut Res 25(14):13439–13445

  21. Ma Z, Guan Y, Liu H, Liu H (2005) Preparation and surface modification of non-porous micro-sized magnetic poly (methyl acrylate) micros-pheres. J Polym Sci A Polym Chem 43:3433–3439

  22. Mahmood A, Malik RM (2014) Human health risk assessment of heavy metals via consumption of contaminated vegetables collected from different irrigation sources in Lahore, Pakistan. Arab J Chem 7:91–99

  23. Mahpishanian S, Sereshti H (2016) Three-dimensional graphene aerogel-supported iron oxide nanoparticles as an efficient adsorbent for magnetic solid phase extraction of organophosphorus pesticide residues in fruit juices followed by gas chromatographic determination. J Chromatogr A 1443:43–53

  24. Mahpishanian S, Sereshti H, Baghdadi M (2015) Superparamagnetic core–shells anchored onto graphene oxide grafted with phenylethyl amine as a nano-adsorbent for extraction and enrichment of organophosphorus pesticides from fruit, vegetable and water samples. J Chromatogr A 1406:48–58

  25. Picó Y, Kozmutza C (2007) Maximum residue levels of pesticides in or on food. Anal Bioanal Chem 389:1805–1814

  26. Rashidi Nodeh H, Wan Ibrahim WA, Kamboh MA, Sanagi MM (2017) New magnetic graphene-based inorganic–organic sol-gel hybrid nanocomposite for simultaneous analysis of polar and non-polar organophosphorus pesticides from water samples using solid-phase extraction. Chemosphere 166:21–30

  27. Šafařı́ková M, Šafařı́k I (1999) Magnetic solid phase extraction. J Magn Magn Mater 194(1):108–112

  28. Sanagi MM, Salleh S, Wan Ibrahim WA, Naim AA, Hermawan D, Miskam M, Aboul-Enein HY (2013) Molecularly imprinted polymer solid phase extraction for the analysis of organophosphorus pesticides in fruit samples. J Food Compos Anal 32(2):155–116

  29. Sargin I, Arslan G (2015) Chitosan/sporopollenin microcapsules: preparation, characterization and application in heavy metals removal. Int J Biol Macromol 75:230–238

  30. Sitko R, Zawisza B, Malicka E (2013) Graphene as a new sorbent in analytical chemistry. TrAC Trends Anal Chem 51(0):33–43

  31. Sun J, Liang Q, Han Q, Zhang X, Dingin M (2015) One-step synthesis of magnetic graphene oxide nanocomposite and its application in magnetic solid phase extraction of heavy metal ions from biological samples. Talanta 132:557–563

  32. Tankiewicz M, Fenik J, Biziuk M (2010) Determination of organophosphorus and organonitrogen pesticides in water samples. TrAC Trends Anal Chem 29:1050–1063

  33. Wan Ibrahim WA, Farhani H, Sanagi MM, Aboul-Enein HY (2010) Solid phase microextraction using new sol–gel hybrid polydimethylsiloxane-2-hydroxymethyl-18-crown-6 coated fiber for determination of organophosphorous pesticides. J Chromatogr A 1217:4890–4897

  34. Wan Ibrahim WA, Ismail WNW, Keyon ASA, Sanagi MM (2011) Preparation and characterization of a new sol-gel hybrid based on tetraetho-xysilane-polydimethylsiloxane as a stir bar extraction sorbent materials. J Sol-Gel Sci Technol 58(3):602–611

  35. Wan Ibrahim WA, Veloo KV, Sanagi MM (2012) Novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane as solid phase extraction sorbent for organophosphorus pesticides. J Chromatogr A 1229:55–62

  36. World Health Organisation (1990) Public health impact of pesticides uses in agriculture. 924 1561,94, 21–32. http://www.who.int/iris/handle/10665/39772

  37. Wu Q, Zhao G, Feng C, Wang C, Wang Z (2011) Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples. J Chromatogr A 1218(44):7936–7942

  38. Xu B, Wang Y, Jin R, Li X, Song D, Zhang H, Sun Y (2015) Magnetic solid phase extraction based on Fe3O4@ polyaniline particles followed by ultrafast liquid chromatography for determination of Sudan dyes in environmental water samples. Anal Methods 7(4):1606–1614

  39. Yusuff AS, Gbadamosi AO, Lala MA, Ngochindo JM (2018) Synthesis and characterization of anthill-eggshell composite adsorbent for removal of hexavlent chromium from aqueous solution. Environ Sci Pollut Res 1–12. https://doi.org/10.1007/s11356-018-2075-2

  40. Zheng Z, Li H, Liu T, Cao R (2010) Monodisperse noble metal nanoparticles stabilized in SBA-15: synthesis, characterisation, and application in microwave-assisted Suzuku-Miyaura coupling reation. J Catal 270(2):268–274

  41. Zheng HB, Zhao Q, Mo JZ, Huang YQ, Luo YB, Yu QW, Feng YQ (2013) Quick, easy, cheap, effective, rugged and safe method with magnetic graphitized carbon black and primary secondary amine as adsorbent and its application in pesticide residue analysis. J Chromatogr A 1300(0):127–133

  42. Zhou Q, Fang Z (2015) Graphene-modified TiO2 nanotube arrays as an adsorbent in micro solid phase extraction for determination of carbamate pestici-des in water samples. Anal Chim Acta 869:43–49

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Funding

One of the authors, Ayuba Markus, would like to convey a profound gratitude and sincere appreciation to Kaduna State Scholarship Board (KSSB), Nigeria, for financial support.

Author information

Correspondence to Afeez O. Gbadamosi.

Additional information

Responsible editor: Tito Roberto Cadaval Jr

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Markus, A., Gbadamosi, A.O., Yusuff, A.S. et al. Magnetite-sporopollenin/graphene oxide as new preconcentration adsorbent for removal of polar organophosphorus pesticides in vegetables. Environ Sci Pollut Res 25, 35130–35142 (2018). https://doi.org/10.1007/s11356-018-3402-3

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Keywords

  • Magnetic solid phase extraction
  • Adsorption
  • Pesticides
  • Sporopollenin
  • Graphene oxide
  • Magnetic nanoparticles