Roka Matriksinde Triazin Pestisitlerinin Tayini için QuEChERS Yönteminin d-SPE Aşamasının Doplu Grafen Kullanılarak Modifikasyonu
Year 2025,
Volume: 53 Issue: 4, 57 - 66, 01.10.2025
Timur Tongur
,
Edip Bayram
Abstract
Nitrogen-doped graphene (N-GN) and nitrogen-doped graphene-coated FexOy (Fe-N-GN) were synthesized through a bottom-up process by a solvothermal method and used as QuEChERS sorbents for the determination of four triazine pesticides in arugula matrix. The dispersive-solid phase extraction step of method was optimized and validated by using high pressure liquid chromatography mass spectrometry. Linearity, LOD, LOQ, recovery, accuracy and precision were investigated in scope of validation. According to the results, N-GN and Fe-N-GN were removed the interferences effectively, and provided satisfactory recoveries (75.92%–108.71%) and RSDs (≤12%). Fe-N-GN was resulted higher recovery values for studied pesticides compared to N-GN. The amount of graphene required to remove interferences is found to be less than the frequently used graphitized carbon black in the QuEChERS method.
Project Number
FBA- 2020-5775
References
-
D. Pimentel, Environmental and economic costs of the application of pesticides primarily in the United States, Environ. Dev. Sustain., 7 (2005) 229–252.
-
G.W. Ware, D.M. Whitacre, The Pesticide Book, 6th ed, MeisterPro Information Resources, A division of Meister Media Worldwide, Willoughby, Ohio, USA, 2004.
-
E. Bayram, Electrosorption of aromatic organic acids from aqueous solutions onto granular activated carbon electrodes for water purification, Hacettepe J. Biol. & Chem., 3 (2016) 273–273.
-
F.P. Carvalho, Pesticides, environment, and food safety, Food Energy Secur., 6 (2017) 48–60.
-
S. Mostafalou, M. Abdollahi, Pesticides and human chronic diseases: evidences, mechanisms, and perspectives. Toxicol. Appl. Pharmacol., 268 (2013) 157–177.
-
M. Anastassiades, S.J. Lehotay, D. Stajnbaher, F.J. Schenck, Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce, J. AOAC Int., 86 (2003) 412-431.
-
Q. Zhou, C. Yu, L. Meng, W. Ji, S. Liu, C. Pan, T. Lan, L. Wang, B. Qu, Research progress of applications for nano-materials in improved QuEChERS method, Crit. Rev. Food Sci. Nutr., 64 (2024) 10517-10536.
-
Y.F. Li, L.Q. Qiao, F.W. Li, Y. Ding, Z.J. Yang, M.L. Wang, Determination of multiple pesticides in fruits and vegetables using a modified quick, easy, cheap, effective, rugged and safe method with magnetic nanoparticles and gas chromatography tandem mass spectrometry, J. of Chromatogr. A, 1361 (2014) 77–87.
-
V.C. Fernandes, M. Freitas, J.P.G. Pacheco, J.M. Oliveira, V.F. Domingues, C. Delerue-Matos, Magnetic dispersive micro solid-phase extraction and gas chromatography determination of organophosphorus pesticides in strawberries, J. Chromatogr. A, 1566 (2018) 1–12.
-
L. Yu, G. Guo, J. Zhao, I. Zhao, A. Xia, X. He, C. Xing, L. Dong, F. Wang, Determination of organochlorine pesticides in green leafy vegetable samples via Fe3O4 magnetic nanoparticles modified QuEChERS integrated to dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry. J. Anal. Methods Chem., 13 (2021) 6622063.
-
P. Zhao, L. Wang, J. Luo, J. Li, C. Pan, Determination of pesticide residues in complex matrices using multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction sorbent. J. Sep. Sci., 35 (2012) 153–158.
-
Y. Han, N. Zou, L. Song, Y. Li, Y. Qin, S. Liu, X. Li, C. Pan, Simultaneous determination of 70 pesticide residues in leek, leaf lettuce and garland chrysanthemum using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials, J. Chromatogr. B, 1005 (2015) 56–64.
-
S. Wang, M. Li, X. Li, X. Li, X. Li, S. Li, Q. Zhang, H. Li, A functionalized carbon nanotube nanohybrids-based QuEChERS method for detection of pesticide residues in vegetables and fruits. J. Chromatogr. A, 1631 (2020) 461526.
-
Y. Chen, S. Cao, L. Zhang, C. Xi, X. Li, Z. Chen, G. Wang, Preparation of size-controlled magnetite nanoparticles with a graphene and polymeric ionic liquid coating for the quick, easy, cheap, effective, rugged and safe extraction of preservatives from vegetables, J. Chromatogr. A, 1448 (2016) 9–19.
-
G. Ma, M. Zhang, L. Zhu, H. Chen, X. Liu, C. Lu, Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea, J. Chromatogr. A, 1531 (2018) 22–31.
-
X. Pang, C. Li, C. Zang, L. Guan, P. Zhang, C. Di, N. Zou, B. Li, W. Mu, J. Lin, Simultaneous detection of ten kinds of insecticide residues in honey and pollen using UPLC-MS/MS with graphene and carbon nanotubes as adsorption and purification materials, Environ. Sci. Pollut. Res., 29 (2022) 21826–21838.
-
G. Liu, M. Tian, M. Lu, W. Shi, L. Li, Y. Gao, T. Li, D. Xu, Preparation of magnetic MOFs for use as a solid-phase extraction absorbent for rapid adsorption of triazole pesticide residues in fruits juices and vegetables, J. Chromatogr. B, 1166 (2021) 122500.
-
X. Peng, G.M. Bao, Y.F. Zhong, L. Zhang, K.B. Zeng, J.X. He, W. Xiao, Y.F. Xia, Q. Fan, H.Q. Yuan, Highly sensitive and rapid detection of thiabendazole residues in oranges based on a luminescent Tb3+-functionalized MOF, Food Chem., 343 (2021) 128504.
-
I.A. Senosy, X.Z. Zhang, Z.H. Lu, X.Y. Guan, Z.H. Yang, J.H. Li, H.M. Guo, T.M. Abdelrahman, M. Mmby, A. Gbiliy, Magnetic metal-organic framework MIL-100 (Fe)/polyethyleneimine composite as an adsorbent for the magnetic solid-phase extraction of fungicides and their determination using HPLC-UV, Microchim. Acta, 188 (2021) 33.
-
M.C. Khetagoudar, U. Jinendra, A.P. Kumar, D. Bilehal, S.P. Kollur, Multiresidue pesticide analysis in green chilli using GC–MS/MS using modified QuEChERS method with highly efficient Fe3O4@CFR@GO nanocomposite, Inorg. Chem. Commun., 137 (2022) 109195.
-
A. Geim, K. Novoselov, The rise of graphene, Nature Mater. 6 (2007) 183–191.
-
P. Zhao, L. Wang, L. Zhou, F. Zhang, S. Kang, C. Pan, Multi-walled carbon nanotubes as alternative reversed-dispersive solid phase extraction materials in pesticide multi-residue analysis with QuEChERS method, J. Chromatogr. A, 1225 (2012) 17–25.
-
S. Bhattacharyya, R. Poi, M. Baskey Sen, S. Mandal, D.K. Hazra, R. Karmakar, Efficient fabrication of pH-modified graphene nano-adsorbent for effective determination and monitoring of multi-class pesticide residues in market-fresh vegetables by GC-MS, J. Food Compos. Anal., 118 (2023) 105153.
-
Analytical quality control and method validation procedures for pesticide residues analysis in food and feed, Available online: https://www.eurl-pesticides.eu/userfiles/file/EurlALL/SANTE_11312_2021.pdf (accessed on June 19, 2025)
-
L. Pareja, V. Cesio, H. Heinzen, A.R. Fernández-Alba, Evaluation of various QuEChERS based methods for the analysis of herbicides and other commonly used pesticides in polished rice by LC-MS/MS, Talanta, 83 (2011) 1613–1622.
-
B. Sungur, Ç. Kızıl, E. Bayram, Scalable synthesis of nitrogen and nitrogen–silicon co-doped graphene: SiC4 and SiN1C3 as new active centers for boosting ORR performance, Int. J. Hydrogen Energy, 48 (2023) 17512–17525.
-
E. Bayram, B. Sungur, Preparation of nitrogen-doped graphene with hollow nano-hemispheres from FexOy@Fe-N-GN: Towards high capacity and durable anode for Li-ion batteries by chemical modifications, ChemElectroChem, 10 (2023) e202300252.
-
S. Yadav, A.P. Singh Raman, H. Meena, A.G. Goswami, V. Bhawna, V. Kumar, P. Jain, G. Kumar, M. Sagar, D.K. Rana, I. Bahadur, P. Singh, An update on graphene oxide: Applications and toxicity. ACS Omega, 7 (2022) 35387–35445.
Modification of d-SPE Step of QuEChERS Method by Using Doped Graphene for the Determination of Triazine Pesticides in Arugula Matrix
Year 2025,
Volume: 53 Issue: 4, 57 - 66, 01.10.2025
Timur Tongur
,
Edip Bayram
Abstract
Nitrogen-doped graphene (N-GN) and nitrogen-doped graphene-coated FexOy (Fe-N-GN) were synthesized through a bottom-up process by a solvothermal method and used as QuEChERS sorbents for the determination of four triazine pesticides in arugula matrix. The dispersive-solid phase extraction step of method was optimized and validated by using high pressure liquid chromatography mass spectrometry. Linearity, LOD, LOQ, recovery, accuracy and precision were investigated in scope of validation. According to the results, N-GN and Fe-N-GN were removed the interferences effectively, and provided satisfactory recoveries (75.92%–108.71%) and RSDs (≤12%). Fe-N-GN was resulted higher recovery values for studied pesticides compared to N-GN. The amount of graphene required to remove interferences is found to be less than the frequently used graphitized carbon black in the QuEChERS method.
Supporting Institution
Scientific Research Projects Coordination Unit of Akdeniz University, Turkey
Project Number
FBA- 2020-5775
References
-
D. Pimentel, Environmental and economic costs of the application of pesticides primarily in the United States, Environ. Dev. Sustain., 7 (2005) 229–252.
-
G.W. Ware, D.M. Whitacre, The Pesticide Book, 6th ed, MeisterPro Information Resources, A division of Meister Media Worldwide, Willoughby, Ohio, USA, 2004.
-
E. Bayram, Electrosorption of aromatic organic acids from aqueous solutions onto granular activated carbon electrodes for water purification, Hacettepe J. Biol. & Chem., 3 (2016) 273–273.
-
F.P. Carvalho, Pesticides, environment, and food safety, Food Energy Secur., 6 (2017) 48–60.
-
S. Mostafalou, M. Abdollahi, Pesticides and human chronic diseases: evidences, mechanisms, and perspectives. Toxicol. Appl. Pharmacol., 268 (2013) 157–177.
-
M. Anastassiades, S.J. Lehotay, D. Stajnbaher, F.J. Schenck, Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce, J. AOAC Int., 86 (2003) 412-431.
-
Q. Zhou, C. Yu, L. Meng, W. Ji, S. Liu, C. Pan, T. Lan, L. Wang, B. Qu, Research progress of applications for nano-materials in improved QuEChERS method, Crit. Rev. Food Sci. Nutr., 64 (2024) 10517-10536.
-
Y.F. Li, L.Q. Qiao, F.W. Li, Y. Ding, Z.J. Yang, M.L. Wang, Determination of multiple pesticides in fruits and vegetables using a modified quick, easy, cheap, effective, rugged and safe method with magnetic nanoparticles and gas chromatography tandem mass spectrometry, J. of Chromatogr. A, 1361 (2014) 77–87.
-
V.C. Fernandes, M. Freitas, J.P.G. Pacheco, J.M. Oliveira, V.F. Domingues, C. Delerue-Matos, Magnetic dispersive micro solid-phase extraction and gas chromatography determination of organophosphorus pesticides in strawberries, J. Chromatogr. A, 1566 (2018) 1–12.
-
L. Yu, G. Guo, J. Zhao, I. Zhao, A. Xia, X. He, C. Xing, L. Dong, F. Wang, Determination of organochlorine pesticides in green leafy vegetable samples via Fe3O4 magnetic nanoparticles modified QuEChERS integrated to dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry. J. Anal. Methods Chem., 13 (2021) 6622063.
-
P. Zhao, L. Wang, J. Luo, J. Li, C. Pan, Determination of pesticide residues in complex matrices using multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction sorbent. J. Sep. Sci., 35 (2012) 153–158.
-
Y. Han, N. Zou, L. Song, Y. Li, Y. Qin, S. Liu, X. Li, C. Pan, Simultaneous determination of 70 pesticide residues in leek, leaf lettuce and garland chrysanthemum using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials, J. Chromatogr. B, 1005 (2015) 56–64.
-
S. Wang, M. Li, X. Li, X. Li, X. Li, S. Li, Q. Zhang, H. Li, A functionalized carbon nanotube nanohybrids-based QuEChERS method for detection of pesticide residues in vegetables and fruits. J. Chromatogr. A, 1631 (2020) 461526.
-
Y. Chen, S. Cao, L. Zhang, C. Xi, X. Li, Z. Chen, G. Wang, Preparation of size-controlled magnetite nanoparticles with a graphene and polymeric ionic liquid coating for the quick, easy, cheap, effective, rugged and safe extraction of preservatives from vegetables, J. Chromatogr. A, 1448 (2016) 9–19.
-
G. Ma, M. Zhang, L. Zhu, H. Chen, X. Liu, C. Lu, Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea, J. Chromatogr. A, 1531 (2018) 22–31.
-
X. Pang, C. Li, C. Zang, L. Guan, P. Zhang, C. Di, N. Zou, B. Li, W. Mu, J. Lin, Simultaneous detection of ten kinds of insecticide residues in honey and pollen using UPLC-MS/MS with graphene and carbon nanotubes as adsorption and purification materials, Environ. Sci. Pollut. Res., 29 (2022) 21826–21838.
-
G. Liu, M. Tian, M. Lu, W. Shi, L. Li, Y. Gao, T. Li, D. Xu, Preparation of magnetic MOFs for use as a solid-phase extraction absorbent for rapid adsorption of triazole pesticide residues in fruits juices and vegetables, J. Chromatogr. B, 1166 (2021) 122500.
-
X. Peng, G.M. Bao, Y.F. Zhong, L. Zhang, K.B. Zeng, J.X. He, W. Xiao, Y.F. Xia, Q. Fan, H.Q. Yuan, Highly sensitive and rapid detection of thiabendazole residues in oranges based on a luminescent Tb3+-functionalized MOF, Food Chem., 343 (2021) 128504.
-
I.A. Senosy, X.Z. Zhang, Z.H. Lu, X.Y. Guan, Z.H. Yang, J.H. Li, H.M. Guo, T.M. Abdelrahman, M. Mmby, A. Gbiliy, Magnetic metal-organic framework MIL-100 (Fe)/polyethyleneimine composite as an adsorbent for the magnetic solid-phase extraction of fungicides and their determination using HPLC-UV, Microchim. Acta, 188 (2021) 33.
-
M.C. Khetagoudar, U. Jinendra, A.P. Kumar, D. Bilehal, S.P. Kollur, Multiresidue pesticide analysis in green chilli using GC–MS/MS using modified QuEChERS method with highly efficient Fe3O4@CFR@GO nanocomposite, Inorg. Chem. Commun., 137 (2022) 109195.
-
A. Geim, K. Novoselov, The rise of graphene, Nature Mater. 6 (2007) 183–191.
-
P. Zhao, L. Wang, L. Zhou, F. Zhang, S. Kang, C. Pan, Multi-walled carbon nanotubes as alternative reversed-dispersive solid phase extraction materials in pesticide multi-residue analysis with QuEChERS method, J. Chromatogr. A, 1225 (2012) 17–25.
-
S. Bhattacharyya, R. Poi, M. Baskey Sen, S. Mandal, D.K. Hazra, R. Karmakar, Efficient fabrication of pH-modified graphene nano-adsorbent for effective determination and monitoring of multi-class pesticide residues in market-fresh vegetables by GC-MS, J. Food Compos. Anal., 118 (2023) 105153.
-
Analytical quality control and method validation procedures for pesticide residues analysis in food and feed, Available online: https://www.eurl-pesticides.eu/userfiles/file/EurlALL/SANTE_11312_2021.pdf (accessed on June 19, 2025)
-
L. Pareja, V. Cesio, H. Heinzen, A.R. Fernández-Alba, Evaluation of various QuEChERS based methods for the analysis of herbicides and other commonly used pesticides in polished rice by LC-MS/MS, Talanta, 83 (2011) 1613–1622.
-
B. Sungur, Ç. Kızıl, E. Bayram, Scalable synthesis of nitrogen and nitrogen–silicon co-doped graphene: SiC4 and SiN1C3 as new active centers for boosting ORR performance, Int. J. Hydrogen Energy, 48 (2023) 17512–17525.
-
E. Bayram, B. Sungur, Preparation of nitrogen-doped graphene with hollow nano-hemispheres from FexOy@Fe-N-GN: Towards high capacity and durable anode for Li-ion batteries by chemical modifications, ChemElectroChem, 10 (2023) e202300252.
-
S. Yadav, A.P. Singh Raman, H. Meena, A.G. Goswami, V. Bhawna, V. Kumar, P. Jain, G. Kumar, M. Sagar, D.K. Rana, I. Bahadur, P. Singh, An update on graphene oxide: Applications and toxicity. ACS Omega, 7 (2022) 35387–35445.