Analytical and Bioanalytical Chemistry

, Volume 410, Issue 19, pp 4679–4687 | Cite as

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

  • Elena Fernández
  • Lorena VidalEmail author
  • Antonio CanalsEmail author
Research Paper
Part of the following topical collections:
  1. Ionic Liquids as Tunable Materials in (Bio)Analytical Chemistry


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.

Graphical abstract

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


Magnetic ionic liquid Magnetic headspace single-drop microextraction Thermal desorption-gas chromatography-mass spectrometry Chlorobenzenes Water samples 



Coefficient of variation






1-Ethyl-3-methylimidazolium tetraisothiocyanatocobaltate(II)


Gas chromatography


Ionic liquids


Internal standard


Limit of detection


Limit of quantification


Liquid-phase microextraction


Magnetic headspace single-drop microextraction


Magnetic ionic liquid


Mass spectrometry






Thermal desorption







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).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.

Supplementary material

216_2017_755_MOESM1_ESM.pdf (157 kb)
ESM 1 (PDF 157 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Departamento de Química Analítica, Nutrición y Bromatología e Instituto Universitario de MaterialesUniversidad de AlicanteAlicanteSpain

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