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Fast liquid chromatography-tandem mass spectrometry methodology for the analysis of alkylphenols and their ethoxylates in wastewater samples from the tank truck cleaning industry

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Abstract

A fast methodology to quantify 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) and their mono- and di-ethoxylates was developed, validated, and applied to real wastewater samples. Dispersive liquid-liquid microextraction was employed as a sample preparation step, leading to a pre-concentration factor of roughly 30. Analysis was carried out by liquid chromatography-tandem mass spectrometry with electrospray ionisation in multiple reaction monitoring mode. Average recoveries were generally between 80 and 120% for both the alkylphenols and their mono- and di-ethoxylates in influent and effluent wastewater. A minimum of 5 concentration levels per compound, ranging between 1 and 500 ng/mL, were prepared to construct calibration curves making use of isotopically labelled internal standards. The method presented good linearity and repeatability over the whole range of concentrations. Taking into account the concentration factor, and the recovery of the compounds, lower limits of quantification obtained in effluent wastewater were 0.04 ng/mL for 4-t-OP and 0.14 ng/mL for 4-NP, complying with European regulations, and between 0.03 ng/mL and 0.39 ng/mL for the ethoxylates. In influent wastewater, these limits were slightly higher. The total run time of 5 min for the alkylphenols and 8 min for the ethoxylates ensured high throughput. The developed method was applied to determine 4-t-OP and 4-NP and their mono- and di-ethoxylates in wastewater from several tank truck cleaning companies, which was subjected to ozonation and/or biological treatment. It was demonstrated that ozonation was best applied after the biological treatment, since in this case, the biological treatment could degrade most of the biodegradable organic matter, after which ozone could react directly with the recalcitrant organic pollutants. In this case, the concentrations of the target compounds in the wastewater of the investigated company decreased below the legally allowed concentration of the European water legislation.

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Acknowledgments

Kris Wolfs is kindly acknowledged for his contribution to the scientific discussions regarding this study and Christophe Bries (AB Sciex) for his advice regarding the operation of the LC-MS. Ludovicus Staelens and Johan Nicolai of UCB Pharma (Belgium) are thanked for the kind gift of the triple quadrupole MS.

Funding

This research was funded by the Flemish Government in the form of a technology transfer (TETRA) project (project no.: HBC.2017.0052: “Inteauclean: Integrated wastewater treatment in the tank truck cleaning sector”).

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Authors and Affiliations

  1. Pharmaceutical Analysis, Department of Pharmaceutical and Pharmacological Sciences, KU Leuven, O&N II Herestraat 49, 3000, Leuven, Belgium

    Mélanie Mignot, Alexander Kensert & Deirdre Cabooter

  2. Process and Environmental Technology Lab, Department of Chemical Engineering, KU Leuven, J. De Nayerlaan 5, 2860, Sint-Katelijne-Waver, Belgium

    Maarten Nagels & Raf DewiI

  3. Bio-Chemical Green Engineering & Materials, Faculty of Applied Engineering, University of Antwerp, Salesianenlaan 90, 2660, Antwerp, Belgium

    Sven Poelmans & Jan Dries

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  1. Mélanie Mignot
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Correspondence to Deirdre Cabooter.

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Mignot, M., Nagels, M., Poelmans, S. et al. Fast liquid chromatography-tandem mass spectrometry methodology for the analysis of alkylphenols and their ethoxylates in wastewater samples from the tank truck cleaning industry. Anal Bioanal Chem 411, 1611–1621 (2019). https://doi.org/10.1007/s00216-019-01623-6

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  • DOI: https://doi.org/10.1007/s00216-019-01623-6

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