In-line sequential injection-based hollow-fiber sorptive microextraction as a front-end to gas chromatography–mass spectrometry: a novel fully automatic sample processing technique for residue analysis


A novel and affordable analytical setup is herein reported for automatic flow-through sorptive microextraction of organic contaminants, exploiting polydimethylsiloxane (PDMS) as a front-end to gas chromatography-ion trap-tandem mass spectrometry. The analytical procedure involves a short single-strand PDMS hollow fiber integrated in a sequential injection (SI) network for automatic fluidic handling by programmable flow. The target species are in-line extracted from 10 mL of sample containing 20 % (v/v) methanol followed by elution with a metered volume of organic solvent, which is whereupon quantitatively transferred into the programmed temperature vaporization (PTV) injector of the GC. Diffusional resistance to mass transfer was overcome by effecting the overall concentration and stripping steps at a single PDMS tubing interface. The proof of concept of the novel hyphenated system was demonstrated for extraction and determination of organochlorine pesticides (OCPs), namely, heptachlor, dieldrin, endrin, endosulfan, p,p′-dichlorodiphenyldichloroethane, p,p′-dichlorodiphenyltrichloroethane, dichlorodiphenyldichloroethylene, and endrin ketone, taken as model analytes, in environmental and industrial waters. Four organic solvents with a broad spectrum of polarity were investigated as eluents in the SI-based assembly, namely, ethyl acetate, methyl tert-butyl ether, hexane, and chloroform. Chloroform was proven the most suitable solvent for expedient elution and fast evaporation in the PTV injector. Under the selected experimental variables, limits of detection (signal-to-noise ratio (S/N) = 3) within the range of 0.3–1.1 ng L−1, limits of quantification (S/N = 10) of 1.0–3.6 ng L−1, and method repeatabilities spanning from 1.7 to 4.7 % were obtained for the suite of OCPs. The hyphenated flow analyzer was harnessed to the analysis of samples of varying matrix complexity with good relative recoveries (86–112 %) in drinking water, surface water, and influent and effluent wastewaters, with quantification limits far below those endorsed by WHO and EU drinking water directives setting maximum allowed concentrations at ≤100 ng L−1 OCPs.

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Warunya Boonjob is grateful to Conselleria d’Educació, Cultura i Universitats, Direcció General d’Universitats, Recerca i Transferència del Coneixement from the Government of the Balearic Islands for allocation of a Ph.D. stipend and travel grant for a 3-month research stay at the University of Santiago de Compostela. She also acknowledges financial support from the European Social Fund and the state budget of the Czech Republic (Project no. CZ.1.07/2.3.00/30.0061). This work was funded by the Spanish Ministry of Economy and Competitiveness (MINECO) and FEDER funds through projects CTM2010-17214 and CTQ2010-18927, and the Ramón y Cajal research program. Additional funding was provided by the Galician Government (Xunta de Galicia) through project 10MDS700006PR. The authors thank Dr. V. Cerda for the loan of analytical instrumentation.

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Correspondence to José Benito Quintana or Manuel Miró.

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Boonjob, W., Quintana, J.B., Rodil, R. et al. In-line sequential injection-based hollow-fiber sorptive microextraction as a front-end to gas chromatography–mass spectrometry: a novel fully automatic sample processing technique for residue analysis. Anal Bioanal Chem 405, 8653–8662 (2013).

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  • Sequential injection analysis
  • Polydimethylsiloxane
  • In-line microextraction
  • Gas chromatography–mass spectrometry
  • Organochlorine pesticides