Food Analytical Methods

, Volume 12, Issue 12, pp 2730–2741 | Cite as

Development of an Efficient Sample Preparation Method Based on Homogeneous Liquid-Liquid Extraction Combined with Dispersive Liquid-Liquid Microextraction Solidification of Floating Organic Drop for Trace Analysis of Pesticide Residues in Fruit and Fruit Juice Samples

  • Mir Ali FarajzadehEmail author
  • Ali Sadeghi Alavian
  • Masoumeh Sattari Dabbagh


In this study, a simple and reliable sample preparation method based on an efficient version of homogeneous liquid-liquid extraction combined with dispersive liquid-liquid microextraction solidification of floating organic drop has been introduced to analyze some pesticide residues in fruit and fruit juice samples with gas chromatography-flame ionization detection. Under the optimum experimental conditions, limits of detection and quantification were in the ranges of 0.20–0.60 and 0.66–2.0 μg L−1, respectively. The repeatability of the method was good and the relative standard deviations were less than 7 % for intra- (n = 6) and inter-day (n = 4) precisions at a concentration of 50 μg L−1 of each analyte. High enrichment factors (3265–3728) and extraction recoveries (82–93 %) were obtained. Finally, the method was applied for determination of pesticides in the selected samples and chlorpyrifos was found in strawberry at ng g−1 concentration. Furthermore, no filtration was used in the cases of the fruit samples.


Homogeneous liquid-liquid microextraction Dispersive liquid-liquid microextraction based on solidification of floating organic drop Pesticide Gas chromatography Fruit and fruit juices 



Dispersive liquid-liquid microextraction


Enrichment factor


Extraction recovery


Flame ionization detection


Gas chromatography


Homogeneous liquid-liquid extraction


Liquid-liquid extraction


Limit of detection


Liquid-phase microextraction


Limit of quantification


Mass spectrometry


Relative standard deviation


Solidification of floating organic drop


Solid-phase extraction



The financial support from University of Tabriz is acknowledged.


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. Ali Sadeghi Alavian declares that he has no conflict of interest. Masoumeh Sattari Dabbagh declares that she has no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animals.


  1. Amini T, Hashemi P (2018) Preconcentration and GC–MS determination of caffeine in tea and coffee using homogeneous liquid–liquid microextraction based on solvents volume ratio alteration. J Chromatogr B 1092:252–257CrossRefGoogle Scholar
  2. Anthemidis AN, Adam IS (2009) Development of on-line single-drop micro-extraction sequential injection system for electrothermal atomic absorption spectrometric determination of trace metals. Anal Chim Acta 632:216–220CrossRefGoogle Scholar
  3. Chen H, Chen R, Li S (2010) Low-density extraction solvent-based solvent terminated dispersive liquid–liquid microextraction combined with gas chromatography-tandem mass spectrometry for the determination of carbamate pesticides in water samples. J Chromatogr A 1217:1244–1248CrossRefGoogle Scholar
  4. Costa LG, Giordano G, Guizzetti M, Vitalone A (2008) Neurotoxicity of pesticides: a brief review. Front Biosci 13:1240–1249CrossRefGoogle Scholar
  5. Djozan D, Assadi Y (2004) Modified pencil lead as a new fiber for solid-phase microextraction. Chromatographia 60:313–317Google Scholar
  6. Ebrahimzadeh H, Yamini Y, Kamarei F, Shariati S (2007) Homogeneous liquid–liquid extraction of trace amounts of mononitrotoluenes from waste water samples. Anal Chim Acta 594:93–100CrossRefGoogle Scholar
  7. Fang G, Chen W, Yao Y, Wang J, Qin J, Wang S (2012) Multi-residue determination of organophosphorus and organochlorine pesticides in environmental samples using solid-phase extraction with cigarette filter followed by gas chromatography–mass spectrometry. J Sep Sci 35:534–540CrossRefGoogle Scholar
  8. Farajzadeh MA, Mogaddam MRA, Aghdam SR, Nouri N, Bamorrowat M (2016) Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection. Food Chem 212:198–204CrossRefGoogle Scholar
  9. Farajzadeh MA, Alavian AS, Dabbagh MS (2018) Application of vortex-assisted liquid–liquid microextraction based on solidification of floating organic droplets for determination of some pesticides in fruit juice samples. Anal Methods 10:5842–5850CrossRefGoogle Scholar
  10. Gao Z, Ma X (2011) Speciation analysis of mercury in water samples using dispersive liquid–liquid microextraction combined with high-performance liquid chromatography. Anal Chim Acta 702:50–55CrossRefGoogle Scholar
  11. Gao Y, Sun P (2018) Determination of five pyrethroid pesticides residue in liquid milk by gas chromatography using multi-walled carbon nanotubes as dispersion solid phase extraction sorbent. Acta Chromatogr 30:141–146CrossRefGoogle Scholar
  12. Ghiasvand A, Shadabi S, Mohagheghzadeh E, Hashemi P (2005) Homogeneous liquid–liquid extraction method for the selective separation and preconcentration of ultra trace molybdenum. Talanta 66:912–916CrossRefGoogle Scholar
  13. Khalili-Zanjani MR, Yamini Y, Yazdanfar N, Shariati S (2008) Extraction and determination of organophosphorus pesticides in water samples by a new liquid phase microextraction–gas chromatography–flame photometric detection. Anal Chim Acta 606:202–208CrossRefGoogle Scholar
  14. Khan DA, Bhatti MM, Khan FA, Naqvi ST, Karam A (2008) Adverse effects of pesticides residues on biochemical markers in Pakistani tobacco farmers. Int J Clin Exp Med 1:274PubMedPubMedCentralGoogle Scholar
  15. Kokosa JM, Przyjazny A, Jeannot M (2009) Solvent microextraction: theory and practice. John Wiley & SonsGoogle Scholar
  16. Li S, Gao P, Zhang J, Li Y, Peng B, Gao H, Zhou W (2012) Sequential dispersive liquid–liquid microextraction for the determination of aryloxyphenoxy-propionate herbicides in water. J Sep Sci 35:3389–3395CrossRefGoogle Scholar
  17. Miró M, Estela JM, Cerdà V (2005) Recent advances in on-line solvent extraction exploiting flow injection/sequential injection analysis. Curr Anal Chem 1:329–343CrossRefGoogle Scholar
  18. Murata K, Yokoyama Y, Ikeda S (1972) Homogeneous liquid-liquid extraction method. Extraction of iron (III) thenoyltrifluoroacetonate by propylene carbonate. Anal Chem 44:805–810CrossRefGoogle Scholar
  19. Nieto A, Borrull F, Pocurull E, Marcé RM (2010) Pressurized liquid extraction: a useful technique to extract pharmaceuticals and personal-care products from sewage sludge. TrAC Trends Anal Chem 29:752–764CrossRefGoogle Scholar
  20. Ojeda CB, Rojas FS (2009) Separation and preconcentration by dispersive liquid–liquid microextraction procedure: a review. Chromatographia 69:1149–1159CrossRefGoogle Scholar
  21. Oshite S, Igarashi S (2001) Homogeneous liquid-liquid extraction as preconcentration method using water/tetrabutylammonium bromide/chloroform ternary component system and its application to the flame-less atomic absorption spectrometry. In: Analytical Sciences/Supplements Proceedings of IUPAC International Congress on Analytical Sciences. JSAC, pp 1329–1331Google Scholar
  22. Paleologos EK, Giokas DL, Karayannis MI (2005) Micelle-mediated separation and cloud-point extraction. TrAC Trends Anal Chem 24:426–436CrossRefGoogle Scholar
  23. Pirsaheb M, Fattahi N, Shamsipur M (2013) Determination of organophosphorous pesticides in summer crops using ultrasound-assisted solvent extraction followed by dispersive liquid–liquid microextraction based on the solidification of floating organic drop. Food Control 34:378–385CrossRefGoogle Scholar
  24. Płotka-Wasylka J, Szczepańska N, de la Guardia M, Namieśnik J (2015) Miniaturized solid-phase extraction techniques. TrAC Trends Anal Chem 73:19–38CrossRefGoogle Scholar
  25. Rastegarzadeh S, Pourreza N, Larki A (2014) Dispersive liquid–liquid microextraction for the microvolume spectrophotometric determination of bismuth in pharmaceutical and human serum samples. Anal Methods 6:3500–3505CrossRefGoogle Scholar
  26. 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
  27. Sarafraz-Yazdi A, Assadi H, Wan Ibrahim WA (2012) Determination of triazole fungicides using hollow fiber liquid phase microextraction prior to gas chromatography–mass spectrometry analysis. Ind Eng Chem Res 51:3101–3107CrossRefGoogle Scholar
  28. Takahashi A, Yamaguchi H, Igarashi S (1997) Homogeneous liquid-liquid extraction method for some kinds of high-valence metal ions using desferrioxamine B. Bunseki Kagaku 46:55–58CrossRefGoogle Scholar
  29. Takahashi A, Ueki Y, Igarashi S (1999) Homogeneous liquid–liquid extraction of uranium (VI) from acetate aqueous solution. Anal Chim Acta 387:71–75CrossRefGoogle Scholar
  30. Tobiszewski M, Mechlińska A, Namieśnik J (2010) Green analytical chemistry—theory and practice. Chem Soc Rev 39:2869–2878CrossRefGoogle Scholar
  31. Zahedi MM, Rahimi-Nasrabadi M, Pourmortazavi SM, Koohbijari GRF, Shamsi J, Payravi M (2012) Emulsification-based dispersive liquid microextraction and HPLC determination of carbazole-based explosives. Microchim Acta 179:57–64CrossRefGoogle Scholar
  32. Zanjani MRK, Yamini Y, Shariati S, Jönsson JÅ (2007) A new liquid-phase microextraction method based on solidification of floating organic drop. Anal Chim Acta 585:286–293CrossRefGoogle Scholar
  33. Zhou Q, Liu J, Cai Y, Liu G, Jiang G (2003) Micro-porous membrane liquid–liquid extraction as an enrichment step prior to nonaqueous capillary electrophoresis determination of sulfonylurea herbicides. Microchem J 74:157–163CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

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

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