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Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples

Abstract

A novel method, solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME), was developed for ultra-preconcentration of 10 antibiotics in different environmental water samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry detection. The optimized results were obtained as follows: after being adjusted to pH 4.0, the water sample was firstly passed through PEP-2 column at 10 mL min−1, and then methanol was used to elute the target analytes for the following steps. Dichloromethane was selected as extraction solvent, and methanol/acetonitrile (1:1, v/v) as dispersive solvent. Under optimal conditions, the calibration curves were linear in the range of 1–1000 ng mL−1 (sulfamethoxazole, cefuroxime axetil), 5–1000 ng mL−1 (tinidazole), 10–1000 ng mL−1 (chloramphenicol), 2-1000 ng mL−1 (levofloxacin oxytetracycline, doxycycline, tetracycline, and ciprofloxacin) and 1–400 ng mL−1 (sulfadiazine) with a good precision. The LOD and LOQ of the method were at very low levels, below 1.67 and 5.57 ng mL−1, respectively. The relative recoveries of the target analytes were in the range from 64.16 % to 99.80 % with relative standard deviations between 0.7 and 8.4 %. The matrix effect of this method showed a great decrease compared with solid-phase extraction and a significant value of enrichment factor (EF) compared with dispersive liquid-liquid microextraction. The developed method was successfully applied to the extraction and analysis of antibiotics in different water samples with satisfactory results.

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Acknowledgments

This work was financially supported by the “123” Project of China Environment Protection Foundation (CEPF2013-123-2-8). This work was also supported by the Large Instrument Sharing Service Construction Special of Shenyang Science and Technology Innovation Fund (No. F14-195-4-00) and the National Natural Science Foundation of China (No. 81503029).

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Correspondence to Longshan Zhao.

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Liang, N., Huang, P., Hou, X. et al. Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples. Anal Bioanal Chem 408, 1701–1713 (2016). https://doi.org/10.1007/s00216-015-9284-z

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  • DOI: https://doi.org/10.1007/s00216-015-9284-z

Keywords

  • Antibiotics
  • Dispersive liquid-liquid microextraction
  • Solid-phase extraction
  • Ultra-high performance liquid chromatography-tandem mass spectrometry
  • Water samples