Hybrid flow analyzer for automatic hollow-fiber-assisted ionic liquid-based liquid-phase microextraction with in-line membrane regeneration


The proof-of-concept of a new methodology for in-line hollow-fiber (HF)-assisted three-phase liquid-phase microextraction (LPME) allowing for handling of the feed and acceptor aqueous solutions and of minute volumes of the organic extracting phase in a programmable flow mode is reported in this paper. The flow analyzer fosters in-line anchoring of ionic-liquid-laden extracting solution (10 % (v/v) methyltrioctyl ammonium chloride in kerosene) in the pores of a single-strand microporous polypropylene HF, and regeneration of the liquid-phase membrane itself for each individual analysis cycle in a fully automated mode. Using hexavalent chromium as a model analyte and 1,5-diphenylcarbazide as a chromogenic probe in the acceptor solution, the flow-based HF-LPME hyphenated system was harnessed to the clean-up of troublesome samples (viz., domestic wastewater and soil leachates) with concomitant enrichment of target species. Distinct extraction modes and chemistries were assessed for enhanced Cr(VI) permeability. A single sample plug was subjected to a twofold backward–forward flow extraction so as to decrease the thickness of the boundary layer at the HF shell side for improved extraction efficiency. Under the optimized physicochemical variables, a limit of detection of 4.6 μg L−1 Cr(VI), a dynamic linear range of up to 500 μg L−1 and intermediate precision better than 10 % were obtained for a sample volume of 2.8 mL buffered at pH 4 and a volume of organic extractant of 120 μL, with an enrichment factor of ca. 11 for a sample residence time in the donor compartment of merely 4.5 min. Analyte recoveries in domestic wastewaters were ≥83 % using external calibration with relative standard deviations better than 14 %, thereby demonstrating the expedient clean-up of samples with elevated content of dissolved organic carbon. The automatic HF-LPME method was validated in terms of bias against the SRM 2701 (NIST soil) preceded by the EPA alkaline digestion method 3060A. No significant differences between Cr(VI) concentration as obtained with the automatic HF-LPME system (546 ± 57 mg kg−1) and the certified value (551.2 ± 17.2 mg kg−1, expressed as mean ± combined uncertainty) were encountered at the 0.05 significance level.

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The authors are grateful for the financial support from Thailand Research Fund under the Royal Golden Jubilee Ph.D. Program (PHD/0068/2551) to Sira Nitiyanontakit and Pakorn Varanusupakul. Pakorn Varanusupakul extends his appreciation to the National Research Council of Thailand (NRCT) through the High Throughput Screening/Analysis: Tool for Drug Discovery, Disease Diagnosis and Heath Safety Project. Manuel Miró extends his appreciation to the Spanish Ministry of Economy and Competiveness for financial support through project CTM2010-17214.

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Correspondence to Manuel Miró.

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Nitiyanontakit, S., Varanusupakul, P. & Miró, M. Hybrid flow analyzer for automatic hollow-fiber-assisted ionic liquid-based liquid-phase microextraction with in-line membrane regeneration. Anal Bioanal Chem 405, 3279–3288 (2013). https://doi.org/10.1007/s00216-013-6744-1

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  • Automation
  • Supported liquid membrane
  • Ionic liquid
  • Miniaturization
  • In-line membrane regeneration