Experimental design of switchable solvent–based liquid phase microextraction for the accurate determination of etrimfos from water and food samples at trace levels by GC-MS

  • Merve Fırat
  • Dotse Selali Chormey
  • Sezgin BakırdereEmail author
  • Fatma TurakEmail author


Presented in this study is a simple but efficient switchable polarity solvent microextraction strategy for etrimfos preconcentration from water and food samples for quantification by gas chromatography mass spectrometry. Repeatability of the extraction process and instrumental measurements were enhanced by using deuterated bisphenol A as internal standard. Significant parameters of the extraction method were fitted into an experimental design model to study the effects of parameters on extraction output, as well as mutual effects of combined parameters. The design model was formed with 51 experimented data obtained from the combination of sodium hydroxide volume, switchable solvent volume, and vortex period at three levels. The method was validated by applying optimum conditions attained from the model predictor. The detection limit was found to be 1.3 ng/mL and it corresponded to an enhancement factor of about 54 folds when compared to direct GC-MS measurement. Etrimfos was not detected in the water and food samples tested but the results (92–107%) obtained from spiked recovery experiments established that etrimfos when present in the selected matrices can be accurately and precisely quantified.


Etrimfos Switchable solvent GC-MS QuEChERS Experimental design 


Funding information

This work was supported by Yildiz Technical University (Scientific Research Project, FBA-2017-3169).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Balaguer, P., Delfosse, V., Grimaldi, M., & Bourguet, W. (2017). Structural and functional evidences for the interactions between nuclear hormone receptors and endocrine disruptors at low doses. Comptes Rendus Biologies, 340(9), 414–420. Scholar
  2. Berry, P. (2006). Pesticide residue minimisation crop guide: cereals. Accessed 2 June 2019.
  3. Chen, H., Yin, P., Wang, Q., Jiang, Y., & Liu, X. (2014). A modified QuEChERS sample preparation method for the analysis of 70 pesticide residues in tea using gas chromatography-tandem mass spectrometry. Food Analytical Methods, 7(8), 1577–1587.CrossRefGoogle Scholar
  4. Chormey, D. S., Ozturk Er, E., Erarpat, S., Ozzeybek, G., Ar, B., & Bakirdere, S. (2018). A novel analytical approach for the determination of parathion methyl in water: quadrupole isotope dilution mass spectrometry-dispersive liquid-liquid microextraction using multivariate optimization. [10.1039/C7AN02014G]. Analyst, 143(5), 1141–1146. Scholar
  5. Damalas, C. A., & Eleftherohorinos, I. G. (2011). Pesticide exposure, safety issues, and risk assessment indicators. International Journal of Environmental Research and Public Health, 8(5), 1402–1419. Scholar
  6. Domínguez de María, P. (2017). Chapter 6 - Ionic liquids, switchable solvents, and eutectic mixtures. In F. Pena-Pereira, & M. Tobiszewski (Eds.), The application of green solvents in separation processes (pp. 139-154): Elsevier.Google Scholar
  7. Gangemi, S., Miozzi, E., Teodoro, M., Briguglio, G., De Luca, A., Alibrando, C., et al. (2016). Occupational exposure to pesticides as a possible risk factor for the development of chronic diseases in humans (Review). Molecular Medicine Reports, 14(5), 4475–4488. CrossRefGoogle Scholar
  8. Grung, M., Lin, Y., Zhang, H., Steen, A. O., Huang, J., Zhang, G., & Larssen, T. (2015). Pesticide levels and environmental risk in aquatic environments in China — a review. Environment International, 81, 87–97. Scholar
  9. John, S., Soloman, P. A., & Fasnabi, P. A. (2016). Study on removal of acetamiprid from wastewater by electrocoagulation. Procedia Technology, 24, 619–630. Scholar
  10. Kumar, J., Lind, P. M., Salihovic, S., van Bavel, B., Ingelsson, E., & Lind, L. (2014). Persistent organic pollutants and inflammatory markers in a cross-sectional study of elderly Swedish people: the PIVUS cohort. Environmental Health Perspectives, 122(9), 977–983. Scholar
  11. Lehotay, S. J. (2007). Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. Journal of AOAC International, 90(2), 485–520.Google Scholar
  12. Li, N., Lei, L., Nian, L., Zhang, R., Wu, S., Ren, R., Wang, Y., Zhang, H., & Yu, A. (2013). A modified QuEChERS method for the determination of some herbicides in yogurt and milk by high performance liquid chromatography. Talanta, 105, 219–228.CrossRefGoogle Scholar
  13. Li, Y., Zhang, W., Wang, R.-G., Wang, P.-L., & Su, X.-O. (2015). Development of a efficient and sensitive dispersive liquid-liquid microextraction technique for extraction and preconcentration of 10 β2-agonists in animal urine. PloS one, 10(9), e0137194. Scholar
  14. Li, Z., Smith, K. H., & Stevens, G. W. (2016). The use of environmentally sustainable bio-derived solvents in solvent extraction applications—a review. Chinese Journal of Chemical Engineering, 24(2), 215–220. Scholar
  15. Mamane, A., Baldi, I., Tessier, J.-F., Raherison, C., & Bouvier, G. (2015). Occupational exposure to pesticides and respiratory health. European Respiratory Review, 24(136), 306–319. Scholar
  16. Mbughuni, M. M., Jannetto, P. J., & Langman, L. J. (2016). Mass spectrometry applications for toxicology. EJIFCC, 27(4), 272–287.Google Scholar
  17. Memon, Z. M., Yilmaz, E., & Soylak, M. (2017). Switchable solvent based green liquid phase microextraction method for cobalt in tobacco and food samples prior to flame atomic absorption spectrometric determination. Journal of Molecular Liquids, 229, 459–464. Scholar
  18. Monneret, C. (2017). What is an endocrine disruptor? Comptes Rendus Biologies, 340(9), 403–405. Scholar
  19. Popp, J., Pető, K., & Nagy, J. (2013). Pesticide productivity and food security. A review. [journal article]. Agronomy for Sustainable Development, 33(1), 243–255. Scholar
  20. Slack, G. C., & Snow, N. H. (2007). 8 HPLC sample preparation. In S. Ahuja, & H. Rasmussen (Eds.), Separation Science and Technology (Vol. 8, pp. 237-268): Academic Press.Google Scholar
  21. Soylak, M., Khan, M., & Yilmaz, E. (2016). Switchable solvent based liquid phase microextraction of uranium in environmental samples: a green approach. [10.1039/C5AY02631H]. Analytical Methods, 8(5), 979–986. Scholar
  22. Wei, Z.-F., Wang, X.-Q., Peng, X., Wang, W., Zhao, C.-J., Zu, Y.-G., & Fu, Y. J. (2015). Fast and green extraction and separation of main bioactive flavonoids from Radix Scutellariae. Industrial Crops and Products, 63, 175–181. Scholar
  23. WHO. (2010). The WHO recommended classification of pesticides by hazard and guidelines to classification 2009. Stuttgart: World Health Organization.Google Scholar
  24. Zhao, P., Wang, L., Zhou, L., Zhang, F., Kang, S., & Pan, C. (2012). Multi-walled carbon nanotubes as alternative reversed-dispersive solid phase extraction materials in pesticide multi-residue analysis with QuEChERS method. Journal of Chromatography A, 1225, 17–25.CrossRefGoogle Scholar

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© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Faculty of Art and Science, Chemistry DepartmentYıldız Technical UniversityİstanbulTurkey

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