Food Analytical Methods

, Volume 9, Issue 8, pp 2133–2141 | Cite as

Dispersive Liquid-Liquid Microextraction Combined with Gas Chromatography-Mass Spectrometry for the Determination of Multiple Pesticides in Celery

  • Yaru Wang
  • Xuexue Miao
  • Haifeng Wei
  • Deyun Liu
  • Gaofeng Xia
  • Xiaoyun YangEmail author


A rapid and sensitive method was established to simultaneously determine multiple pesticide residues in celery through gas chromatography-mass spectrometry (GC-MS). Samples were extracted through a modified quick, easy, cheap, effective, robust, and safe method (modified QuEChERS) and then refined and preconcentrated through dispersive liquid-liquid microextraction (DLLME) by using CHCl3 as extractive solvent and acetonitrile (ACN) as dispersive solvent. The main factors, including type of extraction solvent, volume of extraction solvent, volume of dispersive solvent, extraction time, salt concentration, vortex velocity, and pH of aqueous solution, influencing DLLME were initially evaluated by performing single-factor variable experiments; three significant factors, particularly volume of extraction solvent, volume of dispersive solvent, and extraction time, were thoroughly analyzed through response surface methodology. The following optimized extraction conditions were obtained: 100 μL of CHCl3, 900 μL of ACN, and 1.62-min extraction time. The optimized method was validated with average recoveries ranging from 70.8 to 93.2 % (with relative standard deviations of <15 %) at three spiked levels for all of the pesticides. Good linearity with determination coefficients of >0.9974 was obtained on the basis of the matrix-matched calibration curve of each pesticide; limits of detection ranging from 2.4 to 14.2 μg/kg indicated high sensitivity. Malathion with concentrations varying from 0.009 to 0.012 mg/kg was detected in all of the samples; other pesticides were not detected.


Pesticide residue Celery GC-MS QuEChERS DLLME 


Compliance with Ethical Standards


This study was funded by The National Natural Science Foundation of China (31071702).

Conflict of Interest

Yaru Wang declares that she has no conflict of interest. Xuexue Miao declares that she has no conflict of interest. Haifeng Wei declares that he has no conflict of interest. Deyun Liu declares that he has no conflict of interest. Gaofeng Xia declares that he has no conflict of interest. Xiaoyun Yang declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Informed consent is not applicable in this study.


  1. Andraščíková M, Hrouzková S, Cunha SC (2013) Combination of QuEChERS and DLLME for GC-MS determination of pesticide residues in orange samples. Food Addit Contam A 30:286–297CrossRefGoogle Scholar
  2. Asensio-Ramos M, Hernández-Borges J, Borges-Miquel TM, Rodríguez-Delgado MÁ (2011) Ionic liquid-dispersive liquid–liquid microextraction for the simultaneous determination of pesticides and metabolites in soils using high-performance liquid chromatography and fluorescence detection. J Chromatogr A 1218:4808–4816CrossRefGoogle Scholar
  3. Berton P, Martinis EM, Wuilloud RG (2010) Development of an on-line temperature-assisted ionic liquid dispersive microextraction system for sensitive determination of vanadium in environmental and biological samples. J Hazard Mater 176:721–728CrossRefGoogle Scholar
  4. 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 126:1840–1844CrossRefGoogle Scholar
  5. Caballero-Casero N, Ocak M, Ocak Ü, Rubio S (2014) Quick supramolecular solvent-based microextraction for quantification of low curcuminoid content in food. Anal Bioanal Chem 406:2179–2187CrossRefGoogle Scholar
  6. Cunha SC, Fernandes JO (2011) Multipesticide residue analysis in maize combining acetonitrile-based extraction with dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry. J Chromatogr A 1218:7748–7757CrossRefGoogle Scholar
  7. Di MA, Fidente P, Barbini DA, Dommarco R, Seccia S, Morrica P (2006) Application of solid-phase extraction and liquid chromatography-mass spectrometry to the determination of neonicotinoid pesticide residues in fruit and vegetables. J Chromatogr A 1108:1–6CrossRefGoogle Scholar
  8. Farajzadeh MA, Bahram M, Mehr BG, Jönsson JA (2008) Optimization of dispersive liquid–liquid microextraction of copper (II) by atomic absorption spectrometry as its oxinate chelate: application to determination of copper in different water samples. Talanta 75:832–840CrossRefGoogle Scholar
  9. Fernández M, Picó Y, Manes J (2000) Determination of carbamate residues in fruits and vegetables by matrix solid-phase dispersion and liquid chromatography–mass spectrometry. J Chromatogr A 871:43–56CrossRefGoogle Scholar
  10. Gao S, Yang X, Yu W, Liu Z, Zhang H (2012) Ultrasound-assisted ionic liquid/ionic liquid-dispersive liquid–liquid microextraction for the determination of sulfonamides in infant formula milk powder using high-performance liquid chromatography. Talanta 99:875–882CrossRefGoogle Scholar
  11. Lambropoulou DA, Albanis TA (2003) Headspace solid-phase microextraction in combination with gas chromatography-mass spectrometry for the rapid screening of organophosphorus insecticide residues in strawberries and cherries. J Chromatogr A 993:197–203CrossRefGoogle Scholar
  12. Ma H, Li Y, Zhang H, Shah SM, Chen J (2014) Salt-assisted dispersive liquid–liquid microextraction coupled with programmed temperature vaporization gas chromatography–mass spectrometry for the determination of haloacetonitriles in drinking water. J Chromatogr A 1358:14–19CrossRefGoogle Scholar
  13. Matsadiq G, Hu HL, Ren HB, Zhou YW, Liu L, Cheng J (2011) Quantification of multi-residue levels in peach juices, pulps and peels using dispersive liquid–liquid microextraction based on floating organic droplet coupled with gas chromatography-electron capture detection. J Chromatogr B 879:2113–2118CrossRefGoogle Scholar
  14. Melo A, Mansilha C, Pinho O, Ferreira IMPLVO (2013) Analysis of pesticides in tomato combining QuEChERS and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography. Food Anal Method 6:559–568CrossRefGoogle Scholar
  15. Pena MT, Casais MC, Mejuto MC, Cela R (2009) Development of an ionic liquid based dispersive liquid–liquid microextraction method for the analysis of polycyclic aromatic hydrocarbons in water samples. J Chromatogr A 1216:6356–6364CrossRefGoogle Scholar
  16. Pirard C, Widart J, Nguyen BK, Deleuze C, Heudt L, Haubruge E, De Pauw E, Focant JF (2007) Development and validation of a multi-residue method for pesticide determination in honey using on-column liquid–liquid extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1152:116–123CrossRefGoogle Scholar
  17. Qiao F, Zhang X, Wang M, Kang Y (2010) Rapid extraction of imidacloprid in tomatoes by ultrasonic dispersion liquid–liquid microextraction coupled with LC determination. Chromatographia 72:331–335CrossRefGoogle Scholar
  18. Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S (2006) Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A 1116:1–9CrossRefGoogle Scholar
  19. Wang C, Wu Q, Wu C, Wang Z (2011) Application of dispersion–solidification liquid–liquid microextraction for the determination of triazole fungicides in environmental water samples by high-performance liquid chromatography. J Hazard Mater 185:71–76CrossRefGoogle Scholar
  20. Wu C, Liu N, Wu Q, Wang C, Wang Z (2010) Application of ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of some organophosphorus pesticides in water samples. Anal Chim Acta 679:56–62CrossRefGoogle Scholar
  21. Yan H, Wang H, Qiao J, Yang G (2011) Molecularly imprinted matrix solid-phase dispersion combined with dispersive liquid–liquid microextraction for the determination of four Sudan dyes in egg yolk. J Chromatogr A 1218:2182–2188CrossRefGoogle Scholar
  22. You X, Wang S, Liu F, Shi K (2013) Ultrasound-assisted surfactant-enhanced emulsification microextraction based on the solidification of a floating organic droplet used for the simultaneous determination of six fungicide residues in juices and red wine. J Chromatogr A 1300:64–69CrossRefGoogle Scholar
  23. Zawiyah S, Che Man YB, Nazimah SAH, Chin CK, Tsukamoto I, Hamanyza AH, Norhaizan I (2007) Determination of organochlorine and pyrethroid pesticides in fruit and vegetables using sax/psa clean-up column. Food Chem 102:98–103CrossRefGoogle Scholar
  24. Zhang Y, Lee HK (2013) Low-density solvent-based vortex-assisted surfactant-enhanced-emulsification liquid–liquid microextraction combined with gas chromatography–mass spectrometry for the fast determination of phthalate esters in bottled water. J Chromatogr A 1274:28–35CrossRefGoogle Scholar
  25. Zhang S, Yang X, Yin X, Wang C, Wang Z (2012) Dispersive liquid–liquid microextraction combined with sweeping micellar electrokinetic chromatography for the determination of some neonicotinoid insecticides in cucumber samples. Food Chem 133:544–550CrossRefGoogle Scholar
  26. Zhang J, Liang Z, Guo H, Gao P, Lu R, Zhou W, Zhang S, Gao H (2013) Ionic liquid-based totally organic solvent-free emulsification microextraction coupled with high performance liquid chromatography for the determination of three acaricides in fruit juice. Talanta 115:556–562CrossRefGoogle Scholar
  27. Zhou YW, Han LT, Cheng J, Guo F, Zhi XR, Hu HL, Chen G (2011) Dispersive liquid–liquid microextraction based on the solidification of a floating organic droplet for simultaneous analysis of diethofencarb and pyrimethanil in apple pulp and peel. Anal Bioanal Chem 399:1901–1906CrossRefGoogle Scholar
  28. Zhou X, Cao S, Li X, Tang B, Ding X, Xi C, Hu J, Chen Z (2015) Simultaneous determination of 18 preservative residues in vegetables by ultra high performance liquid chromatography coupled with triplequadrupole/linear ion trap mass spectrometry using a dispersive-SPE procedure. J Chromatogr B 989:21–26CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Yaru Wang
    • 1
  • Xuexue Miao
    • 2
  • Haifeng Wei
    • 1
  • Deyun Liu
    • 1
  • Gaofeng Xia
    • 1
  • Xiaoyun Yang
    • 1
    Email author
  1. 1.Key Laboratory of Natural Pesticide and Chemical Biology of the Ministry of EducationSouth China Agricultural UniversityGuangzhouChina
  2. 2.Hunan Rice Research InstituteHunan Academy of Agricultural ScienceChangshaChina

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