Food Analytical Methods

, Volume 12, Issue 2, pp 534–543 | Cite as

Combination of Modified QuEChERS Extraction Method and Dispersive Liquid–Liquid Microextraction as an Efficient Sample Preparation Approach for Extraction and Preconcentration of Pesticides from Fruit and Vegetable Samples

  • Mir Ali FarajzadehEmail author
  • Hessamaddin Sohrabi
  • Ali Mohebbi


In this study, a combination of modified quick easy cheap effective rugged and safe extraction and dispersive liquid–liquid microextraction has been proposed for the extraction and preconcentration of some widely used pesticides (diazinon, chlorpyrifos, penconazole, oxadiazon, and diniconazole) from fruit and vegetable samples prior to their determination by gas chromatography–flame ionization detection. In the proposed method, firstly, an aliquot of sample is crushed and then its refuse and juice are separated by centrifuging. The juice is transferred to a conical glass test tube. Then acetonitrile as an extraction/disperser solvent is added into the tube containing the refuse. The analyte residues are extracted into acetonitrile after vortexing. The obtained acetonitrile is mixed with an extraction solvent (1,2–dibromoethane) at microliter level and rapidly injected into the juice. As a result, a cloudy state is formed, and the tiny droplets of the extractant containing the extracted analytes are sedimented at the bottom of the tube after centrifugation. Finally, an aliquot of the sedimented organic phase is removed and injected into the separation system for the quantitative analysis. In this study, several significant factors affecting the performance of the introduced method were investigated and optimized. Under the optimum experimental conditions, enrichment factors ranged from 240 to 375 for apricot nectar and 96–150 for solid samples. The relative standard deviations were ≤ 7% for intra-(n = 6) and inter-day (n = 4) precisions at a concentration of 100 μg L−1 of each analyte. Limits of detection were in the ranges of 0.27–0.48 μg L−1 in the solution and 0.68–1.2 μg kg−1 in the solid samples. Finally, several fruit and vegetable samples were analyzed by the proposed method, and penconazole was found in grape at μg kg−1 level.


Quick easy cheap effective rugged and safe method Dispersive liquid–liquid microextraction Fruit and vegetable Pesticides Gas chromatography 



Dispersive liquid–liquid microextraction


Enrichment factor


Extraction recovery


Gas chromatography


Limit of detection


Limit of quantification


Mass spectrometry


Quick easy cheap effective rugged and safe


Relative standard deviation



The authors thank the Research Council of University of Tabriz for financial support.


Mir Ali Farajzadeh has received research grants from University of Tabriz.

Compliance with Ethical Standards

Conflict of Interest

Mir Ali Farajzadeh declares that he has no conflict of interest. Hessamaddin Sohrabi declares that he has no conflict of interest. Ali Mohebbi declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animal subjects.

Informed Consent

Not applicable.

Supplementary material

12161_2018_1384_MOESM1_ESM.doc (382 kb)
ESM 1 (DOC 382 kb)


  1. Anastassiades M, Lehotay SJ, Štajnbaher D, Schenck FJ (2003) 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 86:412–431Google Scholar
  2. Cunha S, Fernandes J (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
  3. European Commission (2011) Method validation and quality control procedures for pesticide residues analysis in food and feed. Document No SANCO/12495/2011. Retrieved from qualcontrol_en.pdf. Accessed on 30 July 2018
  4. Farajzadeh MA, Djozan D, Khorram P (2012) Development of a new dispersive liquid–liquid microextraction method in a narrow-bore tube for preconcentration of triazole pesticides from aqueous samples. Anal Chim Acta 713:70–78CrossRefGoogle Scholar
  5. Farajzadeh MA, Feriduni B, Mogaddam MRA (2015) Development of counter current salting-out homogenous liquid–liquid extraction for isolation and preconcentration of some pesticides from aqueous samples. Anal Chim Acta 885:122–131CrossRefGoogle Scholar
  6. Farajzadeh MA, Mohebbi A, Feriduni B (2016) Development of continuous dispersive liquid–liquid microextraction performed in home-made device for extraction and preconcentration of aryloxyphenoxy–propionate herbicides from aqueous samples followed by gas chromatography–flame ionization detection. Anal Chim Acta 920:1–9CrossRefGoogle Scholar
  7. Farajzadeh MA, Mohebbi A, Mogaddam MRA, Davaran M, Norouzi M (2018) Development of salt-induced homogenous liquid–liquid microextraction based on iso-propanol/sodium sulfate system for extraction of some pesticides in fruit juices. Food Anal Methods 11:2497–2507CrossRefGoogle Scholar
  8. Kjærstad MB, Taxvig C, Nellemann C, Vinggaard AM, Andersen HR (2010) Endocrine disrupting effects in vitro of conazole antifungals used as pesticides and pharmaceuticals. Reprod Toxicol 30:573–582CrossRefGoogle Scholar
  9. Lozano A, Rajski Ł, Belmonte–Valles N, Uclés A, Uclés S, Mezcua M, Fernández–Alba AR (2012) Pesticide analysis in teas and chamomile by liquid chromatography and gas chromatography tandem mass spectrometry using a modified QuEChERS method: validation and pilot survey in real samples. J Chromatogr A 1268:109–122CrossRefGoogle Scholar
  10. Mohebbi A, Yaripour S, Farajzadeh MA, Mogaddam MRA (2018) Combination of dispersive solid phase extraction and deep eutectic solvent–based air–assisted liquid–liquid microextraction followed by gas chromatography–mass spectrometry as an efficient analytical method for the quantification of some tricyclic antidepressant drugs in biological fluids. J Chromatogr A Accepted article 1571:84–93. CrossRefGoogle Scholar
  11. Navalon A, Prieto A, Araujo L, Vılchez JL (2002) Determination of oxadiazon residues by headspace solid–phase microextraction and gas chromatography–mass spectrometry. J Chromatogr A 946:239–245CrossRefGoogle Scholar
  12. Payá P, Anastassiades M, Mack D, Sigalova I, Tasdelen B, Oliva J, Barba A (2007) Analysis of pesticide residues using the quick easy cheap effective rugged and safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem 389:1697–1714CrossRefGoogle Scholar
  13. Płotka-Wasylka J, Szczepańska N, de la Guardia M, Namieśnik J (2016) Modern trends in solid phase extraction: new sorbent media. Trends Anal Chem 77:23–43CrossRefGoogle Scholar
  14. Poulsen ME, Hansen HK, Sloth JJ, Christensen HB, Andersen JH (2007) Survey of pesticide residues in table grapes: determination of processing factors, intake and risk assessment. Food Addit Contam 24:886–895CrossRefGoogle Scholar
  15. Ravelo–Pérez LM, Hernández–Borges J, Rodríguez–Delgado MÁ (2008) Multi–walled carbon nanotubes as efficient solid-phase extraction materials of organophosphorus pesticides from apple, grape, orange and pineapple fruit juices. J Chromatogr A 1211:33–42CrossRefGoogle Scholar
  16. Rezaee M, Assadi Y, Hosseini M–RM, 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
  17. Sarafraz-Yazdi A, Amiri A (2010) Liquid-phase microextraction. Trends Anal Chem 29:1–14CrossRefGoogle Scholar
  18. Torbati M, Farajzadeh MA, Torbati M, Nabil AAA, Mohebbi A, Mogaddam MRA (2018) Development of salt and pH–induced solidified floating organic droplets homogeneous liquid–liquid microextraction for extraction of ten pyrethroid insecticides in fresh fruits and fruit juices followed by gas chromatography–mass spectrometry. Talanta 176:565–572CrossRefGoogle Scholar
  19. Wang Y, Wang Z, Zhang H, Shi Y, Ren R, Zhang H, Yu Y (2011) Application of pneumatic nebulization single-drop microextraction for the determination of organophosphorous pesticides by gas chromatography–mass spectrometry. J Sep Sci 34:1880–1885CrossRefGoogle Scholar
  20. Wu Q, Chang Q, Wu C, Rao H, Zeng X, Wang C, Wang Z (2010) Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of carbamate pesticides in water samples by high performance liquid chromatography. J Chromatogr A 1217:1773–1778CrossRefGoogle Scholar
  21. Yao Z–w, Jiang G–b, Liu J–m, Cheng W (2001) Application of solid-phase microextraction for the determination of organophosphorous pesticides in aqueous samples by gas chromatography with flame photometric detector. Talanta 55:807–814CrossRefGoogle Scholar
  22. Zhang J, Liang Z, Li S, Li Y, Peng B, Zhou W, Gao H (2012) In-situ metathesis reaction combined with ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction method for the determination of phenylurea pesticides in water samples. Talanta 98:145–151CrossRefGoogle Scholar
  23. Zhou Q, Bai H, Xie G, Xiao J (2008) Trace determination of organophosphorus pesticides in environmental samples by temperature-controlled ionic liquid dispersive liquid–phase microextraction. J Chromatogr A 1188:148–153CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Analytical Chemistry, Faculty of ChemistryUniversity of TabrizTabrizIran
  2. 2.Engineering FacultyNear East UniversityMersinTurkey

Personalised recommendations