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.
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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
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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).
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Published in the topical collection Ionic Liquids as Tunable Materials in (Bio)Analytical Chemistry with guest editors Jared L. Anderson and Kevin D. Clark
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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
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DOI: https://doi.org/10.1007/s00216-017-0755-2