Food Analytical Methods

, Volume 11, Issue 9, pp 2497–2507 | Cite as

Development of Salt-Induced Homogenous Liquid–Liquid Microextraction Based on iso-Propanol/Sodium Sulfate System for Extraction of Some Pesticides in Fruit Juices

  • Mir Ali Farajzadeh
  • Ali Mohebbi
  • Mohammad Reza Afshar Mogaddam
  • Maryam Davaran
  • Mahdiyeh Norouzi


In the present work, a simple and fast sample pretreatment method based on salt-induced homogenous liquid–liquid microextraction has been proposed for the extraction and preconcentration of some widely used pesticides (diazinon, ametryn, chlorpyrifos, penconazole, oxadiazon, diniconazole, and fenazaquin) from different fruit juice samples prior to gas chromatography-flame ionization detection. Initially, a small volume (microliter level) of an extraction solvent (iso-propanol) is added into an aqueous phase containing the analytes in order to obtain a homogenous solution. Then, a phase separation agent (sodium sulfate) is added into the homogeneous solution. By this action, the extraction solvent releases from the homogenous solution in the form of tiny droplets containing the analytes and collects on the surface of the aqueous phase as a thin film. A home-made device is used to simplify the removal of the collected organic phase. Finally, an aliquot of the collected organic phase is removed and injected into the separation system for analysis. Under the optimum conditions, limits of detection and quantification were obtained at the ranges of 0.22–0.48 and 0.73–1.7 μg L−1, respectively. The enrichment factors and extraction recoveries of the selected pesticides ranged from 410 to 480 and 82 to 96%, respectively. The relative standard deviations were ≤ 7% for intra- (n = 6) and inter-day (n = 4) precisions at a concentration of 10 μg L−1 of each analyte. Finally, the proposed procedure was successfully applied to the analysis of real samples including apple, sour cherry, peach, grape, and orange juices in order to simultaneously determine the seven aforementioned pesticides. The proposed approach is simple, sensitive, rapid, and requires low solvent consumption, which, in the era of green chemistry, represents a significant advantage. This method and the obtained results can contribute in the improvement of food quality as well as monitoring level of pesticide usage in fruit juices.


Pesticides Salt-induced homogeneous liquid–liquid microextraction Fruit juice Gas chromatography 



Enrichment factor


Extraction recovery


Flame ionization detector


Gas chromatography


Liquid–liquid extraction


Limit of detection


Limit of quantification


Linear range


Mass spectrometry


Relative standard deviation


Solid phase extraction



Authors are grateful to Research Council of the University of Tabriz for financial support. Also, the authors are grateful to Mr. Ali Akbar Alizadeh Nabil and Dr. Houshang Ghorbanpour for their help.


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 Mohebbi declares that he has no conflict of interest. Mohammad Reza Afshar Mogaddam declares that he has no conflict of interest. Maryam Davaran declares that she has no conflict of interest. Mahdiyeh Norouzi declares that she has no conflict of interest.

Ethical Approval

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

Informed Consent

Informed consent is not applicable in this study.


  1. Albero B, Sánchez-Brunete C, Tadeo JL (2005) Multiresidue determination of pesticides in juice by solid–phase extraction and gas chromatography–mass spectrometry. Talanta 66:917–924CrossRefGoogle Scholar
  2. Boonchiangma S, Ngeontae W, Srijaranai S (2012) Determination of six pyrethroid insecticides in fruit juice samples using dispersive liquid–liquid microextraction combined with high performance liquid chromatography. Talanta 88:209–215CrossRefGoogle Scholar
  3. Çabuk H, Köktürk M, Ata S (2014) pH–assisted homogeneous liquid–liquid microextraction using dialkylphosphoric acid as an extraction solvent for the determination of chlorophenols in water samples. J Sep Sci 37:1343–1351CrossRefGoogle Scholar
  4. Chen PS, Huang SD (2006) Determination of ethoprop, diazinon, disulfoton and fenthion using dynamic hollow fiber–protected liquid–phase microextraction coupled with gas chromatography–mass spectrometry. Talanta 69:669–675CrossRefGoogle Scholar
  5. Chen B, Wu FQ, Wu WD, Jin BH, Xie LQ, Feng W, Ouyang G (2016) Determination of 27 pesticides in wine by dispersive liquid–liquid microextraction and gas chromatography–mass spectrometry. Microchem J 126:415–422CrossRefGoogle Scholar
  6. Ebrahimpour B, Yamini Y, Esrafili A (2013) Acid–induced homogenous liquid–phase microextraction: application of medium–chain carboxylic acid as extraction phase. J Sep Sci 36:1493–1499CrossRefGoogle Scholar
  7. 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 11 January 2018)
  8. Farajzadeh MA, Djozan DJ, 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
  9. Farajzadeh MA, Afshar Mogaddam MR, Aghanassab M (2016a) Deep eutectic solvent–based dispersive liquid–liquid microextraction. Anal Methods 8:2576–2583CrossRefGoogle Scholar
  10. Farajzadeh MA, Mohebbi A, Feriduni B (2016b) 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
  11. Farajzadeh MA, Shahedi Hojaghan A, Afshar Mogaddam MR (2017) Development of heat–induced homogeneous liquid–liquid microextraction for extraction and preconcentration of neonicotinoid insecticides from fruit juice and vegetable samples. Food Anal Methods 10:3738–3746CrossRefGoogle Scholar
  12. Frías S, Rodríguez M, Conde J, Pérez-Trujillo J (2003) Optimization of a solid–phase microextraction procedure for the determination of triazines in water with gas chromatography–mass spectrometry detection. J Chromatogr A 1007:127–135CrossRefGoogle Scholar
  13. Gonçalves C, Alpendurada MF (2002) Multiresidue method for the simultaneous determination of four groups of pesticides in ground and drinking waters, using solid–phase microextraction–gas chromatography with electron–capture and thermionic specific detection. J Chromatogr A 968:177–190CrossRefGoogle Scholar
  14. Hosseini MH, Rezaee M, Mashayekhi HA, Akbarian S, Mizani F, Pourjavid MR (2012) Determination of polycyclic aromatic hydrocarbons in soil samples using flotation–assisted homogeneous liquid–liquid microextraction. J Chromatogr A 1265:52–56CrossRefGoogle Scholar
  15. Hyötyläinen T, Riekkola ML (2008) Sorbent–and liquid–phase microextraction techniques and membrane–assisted extraction in combination with gas chromatographic analysis: a review. Anal Chim Acta 614:27–37CrossRefGoogle Scholar
  16. Lasarte-Aragonés G, Lucena R, Cárdenas S, Valcárcel M (2015) Use of switchable hydrophilicity solvents for the homogeneous liquid–liquid microextraction of triazine herbicides from environmental water samples. J Sep Sci 38:990–995CrossRefGoogle Scholar
  17. Millán S, Sampedro MC, Unceta N, Goicolea MA, Rodríguez E, Barrio RJ (2003) Coupling solid–phase microextraction and high–performance liquid chromatography for direct and sensitive determination of halogenated fungicides in wine. J Chromatogr A 995:135–142CrossRefGoogle Scholar
  18. 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. Trends Anal Chem 29:752–764CrossRefGoogle Scholar
  19. Plotka-Wasylka J, Szczepańska N, Guardia M, Namieśnik J (2015) Miniaturized solid–phase extraction techniques. Trends Anal Chem 73:19–38CrossRefGoogle Scholar
  20. Sannino A (2007) Determination of three natural pesticides in processed fruit and vegetables using high–performance liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom 21:2079–2086CrossRefGoogle Scholar
  21. Sharma D, Nagpal A, Pakade YB, Katnoria JK (2010) Analytical methods for estimation of organophosphorus pesticide residues in fruits and vegetables: A review. Talanta 82:1077–1089CrossRefGoogle Scholar
  22. Topuz S, Özhan G, Alpertunga B (2005) Simultaneous determination of various pesticides in fruit juices by HPLC–DAD. Food Control 16:87–92CrossRefGoogle Scholar
  23. Wang JH, Zhang YB, Whang XL (2006) Determination of multiclass pesticide residues in apple juice by gas chromatography–mass spectrometry with large–volume injection. J Sep Sci 29:2330–2337CrossRefGoogle Scholar
  24. 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 organophosphorus pesticides by gas chromatography–mass spectrometry. J Sep Sci 34:1880–1885CrossRefGoogle Scholar
  25. Wang J, Chow W, Leung D, Chang J (2012) Application of ultra high–performance liquid chromatography and electrospray ionization quadrupole orbitrap high–resolution mass spectrometry for determination of 166 pesticides in fruits and vegetables. J Agric Food Chem 60:12088–12104CrossRefGoogle Scholar
  26. 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
  27. Yazdanfar N, Yamini Y, Ghambarian M (2014) Homogeneous liquid–liquid microextraction for determination of organochlorine pesticides in water and fruit samples. Chromatographia 77:329–336CrossRefGoogle Scholar
  28. Yogesh B, Dhananjay Kumar T (2010) Development and applications of single–drop microextraction for pesticide residue analysis: a review. J Sep Sci 33:3683–3691CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Mir Ali Farajzadeh
    • 1
    • 2
  • Ali Mohebbi
    • 1
  • Mohammad Reza Afshar Mogaddam
    • 3
    • 4
  • Maryam Davaran
    • 1
  • Mahdiyeh Norouzi
    • 1
  1. 1.Department of Analytical Chemistry, Faculty of ChemistryUniversity of TabrizTabrizIran
  2. 2.Engineering FacultyNear East UniversityNorth CyprusTurkey
  3. 3.Food and Drug Safety Research CenterTabriz University of Medical SciencesTabrizIran
  4. 4.Pharmaceutical Analysis Research CenterTabriz University of Medical SciencesTabrizIran

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