Skip to main content
SpringerLink
Log in

Determination of Five Organochlorine Pesticides Based on GC–MS Coupled with Deep Eutectic Solvent-Modified Magnetic Graphene Oxide-Improved QuEChERS in Vegetables

  • Original
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

A novel deep eutectic solvent-modified magnetic graphene oxide (DES@MGO) was first synthesized. The microscopic structure, composition, and property of the new magnetic adsorbent was characterized. QuChERS-based DES@MGO was first investigated for the removal of impurities from vegetables. Various influencing factors, such as extraction solvent, the mass of anhydrous MgSO4, the mass of adsorbent, and the oscillation time, had been systematically tested. The linearity of the method for analysis of α-HCH, β-HCH, δ-HCH, and p,p'-DDE was between the range of 5–100 μg kg−1, and for analysis of γ-HCH was 10–100 μg·kg−1. The limits of detection, the limits of quantification, and correlation coefficients were 0.3–2.0 μg kg−1, 0.9–6.6 μg kg−1, and 0.9986–0.9997, respectively. In comparison to the traditional purification materials N-propylethylenediamine (PSA) and magnetic graphene oxide (MGO), DES@MGO exhibited superior adsorbent properties and purification performance with more fast adsorption rate, and could effectively remove the majority interfering substances in vegetable extract with achieving good retention of the 5 organochlorine pesticides (OCPs). In the meantime, as a pretreatment material, the DES@MGO showed the advantage of rapid separation with its favorable magnetism. Herein, the method is of easy operation and accurate quantification, which is suitable for the analysis of OCPs in vegetables.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Wang L, Xue C, Zhang YS, Li ZG, Liu C, Pan X, Chen F, Liu Y (2018) Soil aggregate-associated distribution of DDTs and HCHs in farmland and bareland soils in the Danjiangkou Reservoir Area of China. Environ Pollut 243:734–742

    Article  CAS  PubMed  Google Scholar 

  2. Covaciu FD, Floare AV, Magdas DA, David AP, Marincas O (2020) Distribution and fate of persistent organochlorine pesticides on the soil-forage-milk chain in three transylvanian farms. Anal Lett 54(1–2):265–279

    Google Scholar 

  3. Kang YR, Zhang RJ, Yu KF, Han MW, Wang YH, Huang XY, Wang RX, Liu F (2022) First report of organochlorine pesticides (OCPs) in coral tissues and the surrounding airseawater system from the South China sea: distribution, source, and environmental fate. Chemosphere 286(P2):131711–131711

    Article  CAS  PubMed  Google Scholar 

  4. Fang YY, Nie ZQ, Die QQ, Tian YJ, Liu F, He J, Huang QF (2017) Organochlorine pesticides in soil, air and vegetation at and around a contaminated site in southwestern of China: Concentration, transmission and risk evaluation. Chemosphere 178:340–349

    Article  CAS  PubMed  Google Scholar 

  5. Zheng HY, Ding YH, Xue YG, Xiao KY, Zhu JC, Liu YG, Cai MC (2022) Occurrence, seasonal variations, and eco-risk of currently using organochlorine pesticides in surface seawater of the East China Sea and Western Pacific Ocean. Mar Pollut Bull 185(Pt A):114300–114300

    Article  CAS  PubMed  Google Scholar 

  6. Li J, Wang Z, Li JQ, Zhan SH, An YJ, Hao L, Yang XM, Wang C, Wang Z, Wu QH (2022) Novel N-riched covalent organic framework for solid-phase microextraction of organochlorine pesticides in vegetable and fruit samples. Food Chem 388:133007–133007

    Article  CAS  PubMed  Google Scholar 

  7. Wang N, Cui ZW, Wang Y, Zhang JJ (2022) Characteristics and residual health risk of organochlorine pesticides in fresh vegetables in the suburb of Changchun. Northeast China Int J Environ 19(19):12547–12547

    CAS  Google Scholar 

  8. Anastassiades M, Mastovská K, Lehotay SJ (2003) Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides. J Chromatogr A 1015(1):163–184

    Article  CAS  PubMed  Google Scholar 

  9. Henrique PM, de Campos BPA, Reyes RFG, Arisseto BAP (2021) Exploring miniaturized sample preparation approaches combined with LCQToFMS for the analysis of sulfonamide antibiotic residues in meat- and/or egg-based baby foods. Food Chem 366:130587–130587

    Google Scholar 

  10. Areo OM, Abafe OA, Gbashi S, Njobeh PB (2023) Detection of multimycotoxins in rooibos and other consumed teas in South Africa by a modified QuEChERS method and ultrahigh performance liquid chromatography tandem mass spectrometry. Food Chem. https://doi.org/10.1016/J.FOODCONT.2022.109255

    Article  Google Scholar 

  11. Ma S, Han P, Li A, Wang JH, Feng XY, Wang M (2018) Simultaneous determination of trace levels of 12 steroid hormones in soil using modified QuEChERS extraction followed by ultra performance liquid chromatography-tandem mass spectrometry (UPLC–MS/MS). Chromatographia 81(3):435–445

    Article  CAS  Google Scholar 

  12. Temerdashev ZA, Musorina TA, Ovsepyan SK (2022) Determination of polycyclic aromatic hydrocarbons in soils and bottom sediments by gas chromatography-mass spectrometry with QuEChERS sample preparation. J Anal Chem. https://doi.org/10.1134/S1061934822050136

    Article  Google Scholar 

  13. Wang J, Duan HL, Fan L, Zhang J, Zhang ZQ (2020) A magnetic fluorinated multi-walled carbon nanotubesbased QuEChERS method for organophosphorus pesticide residues analysis in Lycium ruthenicum Murr. Food Chem 338:127805–127805

    Article  PubMed  Google Scholar 

  14. Yu TX, Wang T, Huang ZL, Huang NS, Zhang H, Luo ZH, Li H, Ding SJ, Feng WL (2017) Determination of multiple pesticides in human blood using modified QuEChERS method with Fe3O4 magnetic nanoparticles and GC–MS. Chromatographia 80(1):165–170

    Article  CAS  Google Scholar 

  15. Ma GC, Zhang ML, Zhu L, Chen HP, Liu X, Lu CY (2018) Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multipesticide residues analysis of tea. J Chromatogr A 1531:22–31

    Article  CAS  PubMed  Google Scholar 

  16. Ayyıldız MF, Fındıkoğlu MS, Chormey DS, Bakırdere S (2020) A simple and efficient preconcentration method based on vortex assisted reduced graphene oxide magnetic nanoparticles for the sensitive determination of endocrine disrupting compounds in different water and baby food samples by GC-FID. J Food Compos Anal 88(C):103431–103431

    Article  Google Scholar 

  17. Tan P, Sun J, Hu YY, Zheng F, Qi B, Chen YC, Cheng JH (2015) Adsorption of Cu2+, Cd2+ and Ni2+ from aqueous single metal solutions on graphene oxide membranes. J Hazard Mater 297:251–260

    Article  CAS  PubMed  Google Scholar 

  18. Song XL, Lv H, Wang DD, Liao KC, Wu YY, Li GM, Chen Y (2022) Graphene oxide composite microspheres as a novel dispersive solid-phase extraction adsorbent of bisphenols prior to their quantitation by HPLC-mass spectrometry. Microchem J. https://doi.org/10.1016/J.MICROC.2021.106920

    Article  Google Scholar 

  19. Navid L, Maryam E, Shafiee AM, Khosrou A (2017) Dispersion of magnetic graphene oxide nanoparticles coated with a deep eutectic solvent using ultrasound assistance for preconcentration of methadone in biological and water samples followed by GC-FID and GC–MS. Anal Bioanal Chem 409:6113–6121

    Article  Google Scholar 

  20. Dai YT, Spronsen J, Witkamp GJ, Verpoorte R (2013) Choi YH (2013) Natural deep eutectic solvents as new potential media for green technology. Anal Chim Acta 766:61–68

    Article  CAS  PubMed  Google Scholar 

  21. Borandeh S, Abdolmaleki A, Abolmaali SS, Tamaddon AM (2018) Synthesis, structural and in-vitro characterization of β-cyclodextrin grafted l-phenylalanine functionalized graphene oxide nanocomposite: a versatile nanocarrier for pH-sensitive doxorubicin delivery. Carbohyd Polym 201:151–161

    Article  CAS  Google Scholar 

  22. Abdi G, Alizadeh A, Amirian J, Rezaei S, Sharma G (2019) (2019) Polyamine-modified magnetic graphene oxide surface: Feasible adsorbent for removal of dyes. J Mol Liq 289:111118

    Article  CAS  Google Scholar 

  23. Wang L, Huang Y, Sun X, Huang HJ, Liu PB, Zong M, Wang Y (2014) Synthesis and microwave absorption enhancement of graphene@Fe3O4@SiO2@NiO nanosheet hierarchical structures. Nanoscale 6:3157–3164

    Article  CAS  PubMed  Google Scholar 

  24. Arash M, Julker NM, Roberto C, Gabriele C, Paolo T, Thanh TT, Dusan L (2020) Graphene oxide (GO) decorated on multi-structured porous titania fabricated by plasma electrolytic oxidation (PEO) for enhanced antibacterial performance. Mater Design. https://doi.org/10.1016/J.MATDES.2020.109443

    Article  Google Scholar 

  25. Hosseinzadeh H, Ramin S (2018) Effective removal of copper from aqueous solutions by modified magnetic chitosan/graphene oxide nanocomposites. Int J Biol Sci 113:859–868

    CAS  Google Scholar 

  26. Khurana I, Shaw AK, Shaw T, Bharti J, Khurana M, Rai PK (2018) Batch and dynamic adsorption of Eriochrome Black T from water on magnetic graphene oxide: Experimental and theoretical studies. J Environ Chem Eng 6(1):468–477

    Article  CAS  Google Scholar 

  27. Mojtaba S, Mehdi F, Mousavi PSA, Hajir K (2022) Tetraethylenepentamine-enriched magnetic graphene oxide as a novel Cr(VI) removal adsorbent. React Funct Polym. https://doi.org/10.1016/J.REACTFUNCTPOLYM.2022.105410

    Article  Google Scholar 

  28. Marcano Daniela C, Kosynkin Dmitry V, Berlin Jacob M, Sinitskii A, Song ZG, Slesarev A, Alemany Lawrence B, Liu W, Tour James M (2010) Improved synthesis of graphene oxide. ACS Nano 4(8):4806–4814

    Article  CAS  PubMed  Google Scholar 

  29. Pennante B, David M, SongHee R, GeunHyoung C, SangWon P, ByungSeok K, Hyo KJ, HyoSub L (2021) A comparison of the effectiveness of QuEChERS, FaPEx and a modified QuEChERS method on the determination of organochlorine pesticides in ginseng. PLoS ONE 16(1):e0246108–e0246108

    Article  Google Scholar 

Download references

Funding

This work was supported by Science and Technology Research Project of colleges and universities in Hebei Province, China (QN2023074), key research and development projects in Xingtai, Hebei Province, China, and special project in the field of social development (2022zz049).

Author information

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Xingtai University, Xingtai, 054001, China

    Ling Yu, Shujiao Zhang, Xu He, Jie Hu, Zhiju Zhao, Aiqing Xia, Cuijuan Xing, Ruibing Zhao & Jiawei Zhang

Authors
  1. Ling Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shujiao Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xu He
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jie Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhiju Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Aiqing Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Cuijuan Xing
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ruibing Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Jiawei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Ling Yu: Investigation, Experimental, Data Curation, Writing-Original Draft, Writing-Review & Editing, Supervision, Funding acquisition. Shujiao Zhang: Investigation, Validation, Formal analysis, Writing-Review & Editing, Supervision. Xu He: Data Curation, Conceptualization, Formal analysis, Writing-Review & Editing. Jie Hu: Methodology, Investigation, Software, Visualization, Data curation. Zhiju Zhao: Conceptualization, Methodology, Investigation, Validation, Formal analysis. Aiqing Xia: Methodology, Investigation, Software, Validation, Formal analysis. Cuijuan Xing: Visualization, Methodology, Investigation, Validation. Ruibing Zhao: Investigation, Formal analysis, Validation. Jiawei Zhang: Investigation, Formal analysis, Validation. All authors read and approved the final manuscript.

Corresponding authors

Correspondence to Ling Yu or Shujiao Zhang.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yu, L., Zhang, S., He, X. et al. Determination of Five Organochlorine Pesticides Based on GC–MS Coupled with Deep Eutectic Solvent-Modified Magnetic Graphene Oxide-Improved QuEChERS in Vegetables. Chromatographia 86, 511–522 (2023). https://doi.org/10.1007/s10337-023-04263-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-023-04263-2

Keywords

Search

Navigation