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Preparation of silica-supported carbon by Kraft lignin pyrolysis, and its use in solid-phase extraction of fluoroquinolones from environmental waters

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Abstract

The article describes a carbon-based material for solid-phase extraction (SPE) of fluoroquinolones from waters. It was obtained by pyrolytic deposition of Kraft lignin (LG) on silica particles. Marbofloxacin (MAR) and enrofloxacin (ENR) were chosen as model contaminants. The material was prepared by first adsorbing LG onto silica microparticles, this followed by pyrolytic treatment at 1200 °C for 2 h. Silica-supported carbon was characterized by scanning electron microscopy, surface area measurement (by BET), thermogravimetric analysis, and electron paramagnetic resonance. The carbon-coated silica particles were then tested as a column packing for SPE of MAR and ENR from spiked tap and river waters. Quantitative adsorption was observed at pH values of ~7.5 for both drugs. They were eluted with a 70:30 mixture of aqueous tetrabutylammonium hydroxide and acetonitrile and then quantified by HPLC coupled to fluorescence detection. Samples spiked with MAR and ENR in the range from 10 to 1000 ng·L−1 gave recoveries ranging from 70 to 116% (for n = 3). Good inter-day precision (with RSDs between 7 and 16%) was observed for 20–1000 ng·L−1 spikes, also in natural river water. Sample volumes up to 500 mL provided enrichment factors up to 125, and this makes this material useful for determination of the two drugs at environmentally significant levels which are as low as a few ng·L−1. The batch-to-batch reproducibility was verified for 3 preparations. The sorbent was successfully applied to the determination of these drugs in environmental waters.

Silica-supported carbon from pyrolysis of low-cost biomass (Kraft lignin) is employed for solid-phase extraction of Marbofloxacin and Enrofloxacin from natural waters. Pre-concentration followed by HPLC-FD analysis allows determination of these fluoroquinolone antibiotics at the low nanograms per liter levels.

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Acknowledgments

The Authors want to thank Prof. Chiara Milanese and Dr. Alberto Zeffiro (Department of Chemistry, University of Pavia) for their support in material characterization.

The Authors acknowledge the European Union for an ERASMUS MUNDUS Action 2 scholarship through the PANACEA project Agreement Number 2012 - 2647 / 001 - 001 - EMA2 (European Commission) (D. Vadivel fellowship).

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Authors and Affiliations

  1. Department of Chemistry, University of Pavia, via Taramelli 12, 27100, Pavia, Italy

    Andrea Speltini, Michela Sturini, Federica Maraschi, Elettra Mandelli, Dhanalakshmi Vadivel, Daniele Dondi & Antonella Profumo

  2. Department of Chemistry, Bharathiar University, Coimbatore, 641046, India

    Dhanalakshmi Vadivel

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  1. Andrea Speltini
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Correspondence to Andrea Speltini.

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Speltini, A., Sturini, M., Maraschi, F. et al. Preparation of silica-supported carbon by Kraft lignin pyrolysis, and its use in solid-phase extraction of fluoroquinolones from environmental waters. Microchim Acta 183, 2241–2249 (2016). https://doi.org/10.1007/s00604-016-1859-7

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  • DOI: https://doi.org/10.1007/s00604-016-1859-7

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