Skip to main content
Log in

Hydrophilic magnetic ionic liquid for magnetic headspace single-drop microextraction of chlorobenzenes prior to thermal desorption-gas chromatography-mass spectrometry

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

A new, fast, easy to handle, and environmentally friendly magnetic headspace single-drop microextraction (Mag-HS-SDME) based on a magnetic ionic liquid (MIL) as an extractant solvent is presented. A small drop of the MIL 1-ethyl-3-methylimidazolium tetraisothiocyanatocobaltate(II) ([Emim]2[Co(NCS)4]) is located on one end of a small neodymium magnet to extract nine chlorobenzenes (1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, and pentachlorobenzene) as model analytes from water samples prior to thermal desorption-gas chromatography-mass spectrometry determination. A multivariate optimization strategy was employed to optimize experimental parameters affecting Mag-HS-SDME. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; MIL volume, 1 μL; extraction time, 10 min; stirring speed, 1500 rpm; and ionic strength, 15% NaCl (w/v)), obtaining a linear response from 0.05 to 5 μg L−1 for all analytes. The repeatability of the proposed method was evaluated at 0.7 and 3 μg L−1 spiking levels and coefficients of variation ranged between 3 and 18% (n = 3). Limits of detection were in the order of nanograms per liter ranging from 4 ng L−1 for 1,4-dichlorobenzene and 1,2,3,4-tetrachlorobenzene to 8 ng L−1 for 1,2,4,5-tetrachlorobenzene. Finally, tap water, pond water, and wastewater were selected as real water samples to assess the applicability of the method. Relative recoveries varied between 82 and 114% showing negligible matrix effects.

Magnetic headspace single-drop microextraction followed by thermal desorption-gas chromatography-mass spectrometry

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

Abbreviations

CV:

Coefficient of variation

DBB:

Dibromobenzene

DCB:

Dichlorobenzene

[Emim]2[Co(NCS)4]:

1-Ethyl-3-methylimidazolium tetraisothiocyanatocobaltate(II)

GC:

Gas chromatography

ILs:

Ionic liquids

IS:

Internal standard

LOD:

Limit of detection

LOQ:

Limit of quantification

LPME:

Liquid-phase microextraction

Mag-HS-SDME:

Magnetic headspace single-drop microextraction

MIL:

Magnetic ionic liquid

MS:

Mass spectrometry

PeCB:

Pentachlorobenzene

TCB:

Trichlorobenzene

TD:

Thermal desorption

TeCB:

Tetrachlorobenzene

TG:

Thermogravimetry

References

  1. Sun P, Armstrong DW. Ionic liquids in analytical chemistry. Anal Chim Acta. 2010;661:1–16.

    Article  CAS  PubMed  Google Scholar 

  2. Aguilera-Herrador E, Lucena R, Cárdenas S, Valcárcel M. The roles of ionic liquids in sorptive microextraction techniques. Trends Anal Chem. 2010;29:602–16.

    Article  CAS  Google Scholar 

  3. Zhou Q, Bai H, Xie G, Xiao J. Temperature-controlled ionic liquid dispersive liquid phase micro-extraction. J Chromatogr A. 2008;1177:43–9.

    Article  CAS  PubMed  Google Scholar 

  4. Baghdadi M, Shemirani F. In situ solvent formation microextraction based on ionic liquids: a novel sample preparation technique for determination of inorganic species in saline solutions. Anal Chim Acta. 2009;634:186–91.

    Article  CAS  PubMed  Google Scholar 

  5. Yao C, Anderson JL. Dispersive liquid-liquid microextraction using an in situ metathesis reaction to form an ionic liquid extraction phase for the preconcentration of aromatic compounds from water. Anal Bioanal Chem. 2009;395:1491–502.

    Article  CAS  PubMed  Google Scholar 

  6. Wang Y, Sun Y, Xu B, Li X, Jin R, Zhang H, et al. Magnetic ionic liquid-based dispersive liquid-liquid microextraction for the determination of triazine herbicides in vegetable oils by liquid chromatography. J Chromatogr A. 2014;1373:9–16.

    Article  CAS  PubMed  Google Scholar 

  7. Wang Y, Sun Y, Xu B, Li X, Wang X, Zhang H, et al. Matrix solid-phase dispersion coupled with magnetic ionic liquid dispersive liquid-liquid microextraction for the determination of triazine herbicides in oilseeds. Anal Chim Acta. 2015;888:67–74.

    Article  CAS  PubMed  Google Scholar 

  8. Clark KD, Nacham O, Yu H, Li T, Yamsek MM, Ronning DR, et al. Extraction of DNA by magnetic ionic liquids: tunable solvents for rapid and selective DNA analysis. Anal Chem. 2015;87:1552–9.

    Article  CAS  PubMed  Google Scholar 

  9. Wang X, Xu G, Chen P, Liu X, Fang Y, Yang S, et al. Arsenic speciation analysis in environmental water, sediment and soil samples by magnetic ionic liquid-based air-assisted liquid-liquid microextraction. RSC Adv. 2016;6:110247–54.

    Article  CAS  Google Scholar 

  10. Chatzimitakos T, Binellas C, Maidatsi K, Stalikas C. Magnetic ionic liquid in stirring-assisted drop-breakup microextraction: proof-of-concept extraction of phenolic endocrine disrupters and acidic pharmaceuticals. Anal Chim Acta. 2016;910:53–9.

    Article  CAS  PubMed  Google Scholar 

  11. Trujillo-Rodríguez MJ, Nacham O, Clark KD, Pino V, Anderson JL, Ayala JH, et al. Magnetic ionic liquids as non-conventional extraction solvents for the determination of polycyclic aromatic hydrocarbons. Anal Chim Acta. 2016;934:106–13.

    Article  CAS  PubMed  Google Scholar 

  12. Yu H, Merib J, Anderson JL. Faster dispersive liquid-liquid microextraction methods using magnetic ionic liquids as solvents. J Chromatogr A. 2016;1463:11–9.

    Article  CAS  PubMed  Google Scholar 

  13. An J, Rahn KL, Anderson JL. Headspace single drop microextraction versus dispersive liquid-liquid microextraction using magnetic ionic liquid extraction solvents. Talanta. 2017;167:268–78.

    Article  CAS  PubMed  Google Scholar 

  14. Chisvert A, Benedé JL, Anderson JL, Pierson SA, Salvador A. Introducing a new and rapid microextraction approach based on magnetic ionic liquids: stir bar dispersive liquid microextraction. Anal Chim Acta. 2017;983:130–40.

    Article  CAS  PubMed  Google Scholar 

  15. Benedé JL, Anderson JL, Chisvert A. Trace determination of volatile polycyclic aromatic hydrocarbons in natural waters by magnetic ionic liquid-based stir bar dispersive liquid microextraction. Talanta. 2018;176:253–61.

    Article  CAS  PubMed  Google Scholar 

  16. Trujillo-Rodríguez MJ, Pino V, Anderson JL. Magnetic ionic liquids as extraction solvents in vacuum headspace single-drop microextraction. Talanta. 2017;172:86–94.

    Article  CAS  PubMed  Google Scholar 

  17. Clark KD, Nacham O, Purslow JA, Pierson SA, Anderson JL. Magnetic ionic liquids in analytical chemistry: a review. Anal Chim Acta. 2016;934:9–21.

    Article  CAS  PubMed  Google Scholar 

  18. Rezaee M, Assadi Y, Milani Hosseini M-R, Aghaee E, Ahmadi F, Berijani S. Determination of organic compounds in water using dispersive liquid-liquid microextraction. J Chromatogr A. 2006;1116:1–9.

    Article  CAS  PubMed  Google Scholar 

  19. Jeannot MA, Cantwell FF. Mass transfer characteristics of solvent extraction into a single drop at the tip of a syringe needle. Anal Chem. 1997;69:235–9.

    Article  CAS  Google Scholar 

  20. Chisvert A, Román IP, Vidal L, Canals A. Simple and commercial readily-available approach for the direct use of ionic liquid-based single-drop microextraction prior to gas chromatography. Determination of chlorobenzenes in real water samples as model analytical application. J Chromatogr A. 2009;1216:1290–5.

    Article  CAS  PubMed  Google Scholar 

  21. Vidal L, Domini CE, Grané N, Psillakis E, Canals A. Microwave-assisted headspace single-drop microextraction of chlorobenzenes from water samples. Anal Chim Acta. 2007;592:9–15.

    Article  CAS  PubMed  Google Scholar 

  22. Vidal L, Psillakis E, Domini CE, Grané N, Marken F, Canals A. An ionic liquid as a solvent for headspace single drop microextraction of chlorobenzenes from water samples. Anal Chim Acta. 2007;584:189–95.

    Article  CAS  PubMed  Google Scholar 

  23. Zhao F, Lu S, Du W, Zeng B. Ionic liquid-based headspace single-drop microextraction coupled to gas chromatography for the determination of chlorobenzene derivatives. Microchim Acta. 2009;165:29–33.

    Article  CAS  Google Scholar 

  24. Malcom HM, Howe PD, Dobson S. Chlorobenzenes other than hexachlorobenzene: environmental aspects. In: Concise International Chemical Assessment Documents. 2004. http://www.inchem.org/documents/cicads/cicads/cicad60.htm. Accesed 26 Oct 2017.

  25. U.S. Department of Health and Human Servicies. 14th report on carcinogens. 2016. https://ntp.niehs.nih.gov/pubhealth/roc/index-1.html. Accesed 26 Oct 2017.

  26. Peppel T, Köckerling M, Geppert-Rybczyńska M, Ralys RV, Lehmann JK, Verevkin SP, et al. Low-viscosity paramagnetic ionic liquids with doubly charged [Co(NCS)4]2− ions. Angew Chemie. 2010;49:7116–9.

    Article  CAS  Google Scholar 

  27. Vidal L, Ahmadi M, Fernández E, Madrakian T, Canals A. Magnetic headspace adsorptive extraction of chlorobenzenes prior to thermal desorption gas chromatography-mass spectrometry. Anal Chim Acta. 2017;971:40–7.

    Article  CAS  PubMed  Google Scholar 

  28. Geppert-Rybczyńska M, Lehmann JK, Peppel T, Köckerling M, Heintz A. Studies of physicochemical and thermodynamic properties of the paramagnetic 1-alkyl-3-methylimidazolium ionic liquids (EMIm)2[Co(NCS)4] and (BMIm)2[Co(NCS)4]. J Chem Eng Data. 2010;55:5534–8.

    Article  CAS  Google Scholar 

  29. Santos E, Albo J, Rosatella A, Afonso CAM, Irabien Á. Synthesis and characterization of magnetic ionic liquids (MILs) for CO2 separation. J Chem Technol Biotechnol. 2014;89:866–71.

    Article  CAS  Google Scholar 

  30. Del Sesto RE, McCleskey TM, Burrell AK, Baker GA, Thompson JD, Scott BL, Wilkes JS, Williams P (2008) Structure and magnetic behavior of transition metal based ionic liquids. Chem Commun 447–9.

  31. Montgomery DC. Design and analysis of experiments. 7th ed. New Jersey (USA): Wiley; 2009.

    Google Scholar 

  32. Jeannot MA, Przyjazny A, Kokosa JM. Single drop microextraction—development, applications and future trends. J Chromatogr A. 2010;1217:2326–36.

    Article  CAS  PubMed  Google Scholar 

  33. Miller JN, Miller JC. Statistics and chemometrics for analytical chemistry. 5th ed. London (UK): Pearson Prentice Hall; 2005.

    Google Scholar 

  34. Mackay D, Shiu WY. A critical review of Henry’s law constants for chemicals of environmental interest. J Phys Chem Ref Data. 1981;10:1175–89.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to thank Vicerrectorado de Investigación y Transferencia del Conocimiento of the University of Alicante (UAUSTI16-04), Generalitat Valenciana (project nos. GVA/2014/096 and PROMETEO/2013/038), and Ministerio de Economía, Industria y Competitividad (project no. CTQ2016-79991-R, AEI/FEDER, UE) for the financial support. The authors would also like to thank Dr. Martin Köckerling from the Department of Inorganic Chemistry of the University of Rostock (Germany) for the MIL supply. E. Fernández thanks Ministerio de Educación for her FPU grant (FPU13/03125).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Lorena Vidal or Antonio Canals.

Ethics declarations

Conflict of interest

The authors declare that they have no conflicts of interest.

Additional information

Published in the topical collection Ionic Liquids as Tunable Materials in (Bio)Analytical Chemistry with guest editors Jared L. Anderson and Kevin D. Clark

Electronic supplementary material

ESM 1

(PDF 157 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Fernández, E., Vidal, L. & Canals, A. Hydrophilic magnetic ionic liquid for magnetic headspace single-drop microextraction of chlorobenzenes prior to thermal desorption-gas chromatography-mass spectrometry. Anal Bioanal Chem 410, 4679–4687 (2018). https://doi.org/10.1007/s00216-017-0755-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-017-0755-2

Keywords

Navigation