In-Tube Ultrasound Assisted Dispersive Solid–Liquid Microextraction Based on Self-Assembly and Solidification of an Alkanol-Based Floating Organic Droplet for Determination of Pyrethroid Insecticides in Chrysanthemum

  • Jiaying Xue
  • Dong Zhang
  • Xiangwei Wu
  • Dandan Pan
  • Rimao HuaEmail author


A new in-tube pretreatment method based on ultrasound assisted dispersive solid–liquid microextraction using self-assembly and solidification of an alkanol-based floating organic droplet was developed for the determination of eight pyrethroid insecticides in chrysanthemum by gas chromatography with electron capture detection. This method fully utilized the restricted access property of a 1-decanol/acetonitrile mixture for effective extraction of the analytes from chrysanthemum under ultrasonication, and the self-assembly and coacervation process of 1-decanol by adding water. The 1-decanol phase aggregated and floated on the surface, solidified in an ice bath, and thus was easily collected. For the first time, extraction, separation and preconcentration were combined in a tube, not requiring stepwise preparation for a solid matrix. The recoveries ranged from 75 to 104% with the relative standard deviations of < 8%. The limits of quantification were in the range of 0.15–1.5 µg kg− 1 up to 52-fold compared with the conventional QuEChERS-based, SPE, and solid–liquid dispersive microextraction methods. The results demonstrated that the proposed method was time-saving, sensitive, and environmentally friendly for pyrethroids analysis in chrysanthemum.


In-tube ultrasound assisted dispersive solid–liquid microextraction Alkanol-based composite solvent Self-assembly and solidification Pyrethroids Chrysanthemum 



This work was partly supported by the National Key Research and Development Program of China (2016YFD0200201), the National Natural Science Foundation of China (41807490), the Natural Science Research Project of High Education of Anhui (KJ2018A0128), and the University Youth Science Foundation of Anhui Agricultural University (2017zd04).

Compliance with Ethical Standards

Conflict of interest

Author Jiaying Xue declares that she has no conflict of interest. Author Dong Zhang declares that he has no conflict of interest. Author Xiangwei Wu declares that he has no conflict of interest. Author Dandan Pan declares that she has no conflict of interest. Author Rimao Hua 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.


  1. 1.
    Xue JY, Chen XC, Jiang WQ, Liu FM, Li HC (2015) Rapid and sensitive analysis of nine fungicide residues in chrysanthemum by matrix extraction-vortex-assisted dispersive liquid–liquid microextraction. J Chromatogr B 975:9–17CrossRefGoogle Scholar
  2. 2.
    Xue JY, Xu YJ, Liu FM, Xue J, Li HC, Peng W (2013) Comparison of different sample pre-treatments for multi-residue analysis of organochlorine and pyrethroid pesticides in chrysanthemum by gas chromatography with electron capture detection. J Sep Sci 36:1311–1316CrossRefGoogle Scholar
  3. 3.
    Xue J, Hao LL, Peng F (2008) Residues of 18 organochlorine pesticides in 30 traditional Chinese medicines. Chemosphere 71:1051–1055CrossRefGoogle Scholar
  4. 4.
    Xue JY, Li HC, Liu FM, Xue J, Chen XC, Zhan J (2014) Transfer of difenoconazole and azoxystrobin residues from chrysanthemum flower tea to its infusion. Food Addit Contam Part A 31:666–675CrossRefGoogle Scholar
  5. 5.
    Chen HP, Gao GW, Liu PX, Pan ML, Chai YF, Liu X, Lu CY (2017) Development and validation of an ultra performance liquid chromatography exactive orbitrap mass spectrometry for the determination of fipronil and its metabolites in tea and chrysanthemum. Food Chem 246:328–334CrossRefGoogle Scholar
  6. 6.
    Petrarca MH, Ccanccapa-Cartagena A, Masiá A, Godoy HT, Picó Y (2017) Comparison of green sample preparation techniques in the analysis of pyrethrins and pyrethroids in baby food by liquid chromatography-tandem mass spectrometry. J Chromatogr A 1497:28–37CrossRefGoogle Scholar
  7. 7.
    Ccanccapa-Cartagena A, Masiá A, Picó Y (2017) Simultaneous determination of pyrethroids and pyrethrins by dispersive liquid-liquid microextraction and liquid chromatography triple quadrupole mass spectrometry in environmental samples. Anal Bioanal Chem 409:4787–4799CrossRefGoogle Scholar
  8. 8.
    Amde M, Tan ZQ, Liu R, Liu JF (2015) Nanofluid of zinc oxide nanoparticles in ionic liquid for single drop liquid microextraction of fungicides in environmental waters prior to high performance liquid chromatographic analysis. J Chromatogr A 1395:7–15CrossRefGoogle Scholar
  9. 9.
    Wang HZ, Hu L, Li WZ, Yang XL, Lu RH, Zhang SB, Zhou WF, Gao HX, Li J (2017) In-syringe dispersive liquid-liquid microextraction based on the solidification of ionic liquids for the determination of benzoylurea insecticides in water and tea beverage samples. Talanta 162:625–633CrossRefGoogle Scholar
  10. 10.
    Zhang Y, Zhang X, Jiao B (2014) Determination of ten pyrethroids in various fruit juices: comparison of dispersive liquid-liquid microextraction sample preparation and QuEChERS method combined with dispersive liquid-liquid microextraction. Food Chem 159:367–373CrossRefGoogle Scholar
  11. 11.
    Xue JY, Li HC, Liu FM, Jiang WQ, Chen XC (2014) Determination of strobilurin fungicides in cotton seed by combination of acetonitrile extraction and dispersive liquid-liquid microextraction coupled with gas chromatography. J Sep Sci 37:845–852CrossRefGoogle Scholar
  12. 12.
    Samadi S, Sereshti H, Assadi Y (2012) Ultra-preconcentration and determination of thirteen organophosphorus pesticides in water samples using solid-phase extraction followed by dispersive liquid-liquid microextraction and gas chromatography with flame photometric detection. J Chromatogr A 1219:61–65CrossRefGoogle Scholar
  13. 13.
    Jowkarderis M, Raofie F (2012) Optimization of supercritical fluid extraction combined with dispersive liquid-liquid microextraction as an efficient sample preparation method for determination of 4-nitrotoluene and 3-nitrotoluene in a complex matrix. Talanta 88:50–53CrossRefGoogle Scholar
  14. 14.
    Farajzadeh MA, Djozan D, Nouri N, Bamorowat M, Shalamzari MS (2010) Coupling stir bar sorptive extraction-dispersive liquid-liquid microextraction for pre-concentration of triazole pesticides from aqueous samples followed by GC-FID and GC-MS determinations. J Sep Sci 33:1816–1828CrossRefGoogle Scholar
  15. 15.
    Bazregar M, Rajabi M, Yamini Y, Saffarzadeh Z, Asghari A (2016) Tandem dispersive liquid-liquid microextraction as an efficient method for determination of basic drugs in complicated matrices. J Chromatogr A 1429:13–21CrossRefGoogle Scholar
  16. 16.
    Ballesteros-Gómez A, Rubio S (2012) Environment-responsive alkanol-based supramolecular solvents: Characterization and potential as restricted access property and mixed-mode extractants. Anal Chem 84:342–349CrossRefGoogle Scholar
  17. 17.
    Ballesteros-Gómez A, Lunar L, Sicilia MD, Rubio S (2018) Hyphenating supramolecular solvents and liquid chromatography: tips for efficient extraction and reliable determination of organics. Chromatographia. CrossRefGoogle Scholar
  18. 18.
    Saraji M, Boroujeni MK (2014) Recent developments in dispersive liquid-liquid microextraction. Anal Bioanal Chem 406:2027–2066CrossRefGoogle Scholar
  19. 19.
    Ho Y-M, Tsoi Y-K, Leung KS-Y (2013) Highly sensitive and selective organophosphate screening in twelve commodities of fruits, vegetables and herbal medicines by dispersive liquid–liquid microextraction. Anal Chim Acta 775:58–66CrossRefGoogle Scholar
  20. 20.
    Vera-Avila LE, Rojo-Portillo T, Ovarrubias-Herrera R, Peña-Alvarez A (2013) Capabilities and limitations of dispersive liquid-liquid microextraction with solidification of floating organic drop for the extraction of organic pollutants from water samples. Anal Chim Acta 805:60–69CrossRefGoogle Scholar
  21. 21.
    Bolzan CM, Caldas SS, Guimarães BS, Primel EG (2016) Dispersive liquid-liquid microextraction based on solidification of floating organic droplet for the determination of triazine and triazoles in mineral water samples. J Sep Sci 39:3410–3417CrossRefGoogle Scholar
  22. 22.
    Pirsaheb M, Fattahi N, Shamsipur M, Khodadadi T (2013) Application of dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous determination of alachlor and atrazine in aqueous samples. J Sep Sci 36:684–689CrossRefGoogle Scholar
  23. 23.
    Sanagi MM, Abbas HH, Ibrahim WAW, Aboul-Enien HY (2012) Dispersive liquid-liquid microextraction method based on solidification of floating organic droplet for the determination of triazine herbicides in water and sugarcane samples. Food Chem 133:557–562CrossRefGoogle Scholar
  24. 24.
    Lima DL, Silva CP, Otero M, Esteves VI (2013) Low cost methodology for estrogens monitoring in water samples using dispersive liquid-liquid microextraction and HPLC with fluorescence detection. Talanta 115:980–985CrossRefGoogle Scholar
  25. 25.
    Farajzadeh MA, Afshar Mogaddam MR, 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 Chemi 212:198–204CrossRefGoogle Scholar
  26. 26.
    Mirparizi E, Rajabi M, Bazregar M, Asghari A (2017) Centrifugeless dispersive liquid-liquid microextraction based on salting-out phenomenon as an efficient method for determination of phenolic compounds in environmental samples. Anal Bioanal Chem 409:3007–3016CrossRefGoogle Scholar
  27. 27.
    Chen PS, Haung WY, Huang SD (2014) Analysis of triazine herbicides using an up-and- down-shaker-assisted dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry. J Chromatogr B 955–956:116–123CrossRefGoogle Scholar
  28. 28.
    Lin ZB, Li JL, Zhang XY, Qiu MH, Huang ZB, Rao YL (2017) Ultrasound-assisted dispersive liquid-liquid microextraction for the determination of seven recreational drugs in human whole blood using gas chromatography-mass spectrometry. J Chromatogr B 1046:177–184CrossRefGoogle Scholar
  29. 29.
    Ghazaghi M, Mousavi HZ, Shirkhanloo H, Rashidi A (2017) Stirring-controlled solidified floating solid-liquid drop microextraction as a new solid phase-enhanced liquid-phase microextraction method by exploiting magnetic carbon nanotube-nickel hybrid. Anal Chim Acta 951:78–88CrossRefGoogle Scholar
  30. 30.
    Wang HZ, Hu L, Liu XY, Yin SJ, Lu RH, Zhang SB, Zhou WF, Gao HX (2017) Deep eutectic solvent-based ultrasound-assisted dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the determination of ultraviolet filters in water samples. J Chromatogr A 1516:1–8CrossRefGoogle Scholar
  31. 31.
    Xue JY, Li HC, Liu FM, Jiang WQ, Hou F (2016) Vortex-assisted matrix solid-liquid dispersive microextraction for the analysis of triazole fungicides in cotton seed and honeysuckle by gas chromatography. Food Chem 196:867–876CrossRefGoogle Scholar
  32. 32.
    Qi XY (2010) Development of a matrix solid-phase dispersion-sonication extraction method for the determination of fungicides residues in ginseng extract. Food Chem 121:758–762CrossRefGoogle Scholar
  33. 33.
    Quan C, Shang YG, Li SF, Tang SK, Huang T, Fang X (2010) Kinetic study of supercritical fluid extraction of organochlorine pesticides from ginseng by Simulink simulation. J Taiwan Inst Chem Eng 41:44–48CrossRefGoogle Scholar
  34. 34.
    Huang XH, Zhao XH, Lu XT, Tian HP, Xu AJ, Liu Y, Jian Z (2014) Simultaneous determination of 50 residual pesticides in flos chrysanthemi using accelerated solvent extraction and gas chromatography. J Chromatogr B 967:1–7CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Jiaying Xue
    • 1
  • Dong Zhang
    • 1
  • Xiangwei Wu
    • 1
  • Dandan Pan
    • 1
  • Rimao Hua
    • 1
    Email author
  1. 1.College of Resources and Environment, Key Laboratory of Agri-food Safety of Anhui ProvinceAnhui Agricultural University, Key Laboratory of Agri-food Safety of Anhui ProvinceHefeiPeople’s Republic of China

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