Analytical and Bioanalytical Chemistry

, Volume 411, Issue 8, pp 1611–1621 | Cite as

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

  • Mélanie Mignot
  • Maarten Nagels
  • Sven Poelmans
  • Alexander Kensert
  • Jan Dries
  • Raf DewiI
  • Deirdre CabooterEmail author
Research Paper


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.


Alkylphenol Alkylphenol ethoxylate Dispersive liquid-liquid microextraction Liquid chromatography-tandem mass spectrometry Wastewater Tank truck cleaning sector 



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 information

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”).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2019_1623_MOESM1_ESM.pdf (239 kb)
ESM 1 (PDF 239 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Mélanie Mignot
    • 1
  • Maarten Nagels
    • 2
  • Sven Poelmans
    • 3
  • Alexander Kensert
    • 1
  • Jan Dries
    • 3
  • Raf DewiI
    • 2
  • Deirdre Cabooter
    • 1
    Email author
  1. 1.Pharmaceutical Analysis, Department of Pharmaceutical and Pharmacological SciencesKU LeuvenLeuvenBelgium
  2. 2.Process and Environmental Technology Lab, Department of Chemical EngineeringKU LeuvenSint-Katelijne-WaverBelgium
  3. 3.Bio-Chemical Green Engineering & Materials, Faculty of Applied EngineeringUniversity of AntwerpAntwerpBelgium

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