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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

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

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.

Keywords

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

Notes

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 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)

References

  1. 1.
    Salgueiro-González N, Muniategui-Lorenzo S, López-Mahía P, Prada-Rodríguez D. Trends in analytical methodologies for the determination of alkylphenols and bisphenol A in water samples. Anal Chim Acta. 2017;962:1–14.Google Scholar
  2. 2.
    Pothitou P, Voutsa D. Endocrine disrupting compounds in municipal and industrial wastewater treatment plants in Northern Greece. Chemosphere. 2008;73:1716–23.Google Scholar
  3. 3.
    Substance evaluation conclusion and evaluation report for nonylphenol, branched, ethoxylated. 2016. Online available: https://echa.europa.eu/documents/10162/13628/SEV-500-209-1-1_CONCLUSION_AND_REPORT_public_7547_en.pdf/34bf9b62-1499-18af-b059-4c8581b030cd. [Accessed 18 11 2018].
  4. 4.
    Caluwé M, Dobbeleers T, Daens D, Geuens L, Blust R, Dries J. SBR treatment of tank truck cleaning wastewater: sludge characteristics, chemical and ecotoxicological effluent quality. Environ Technol. 2018;39:2524–33.Google Scholar
  5. 5.
    Dries J, De Schepper W, Geuens L, Blust R. Removal of ecotoxicity and COD from tank truck cleaning wastewater. Water Sci Technol. 2013;68:2202–7.Google Scholar
  6. 6.
    Bennie D. Review of the environmental occurrence of alkylphenols andalkylphenol ethoxylates. Water Qual Res J Can. 1999;34:79–122.Google Scholar
  7. 7.
    Soares A, Guieysse B, Jefferson B, Cartmell E, Leste J. Nonylphenol in the environment: a critical review on occurrence, fate, toxicity and treatment in wastewaters. Environ Int. 2008;34:1033–49.Google Scholar
  8. 8.
    Ying GG, Williams B, Kookana R. Environmental fate of alkylphenols andalkylphenol ethoxylates – a review. Environ Int. 2002;28:215–26.Google Scholar
  9. 9.
    Sacco C, Pizzo A, Tiscione E, Burrini D, Messeri L, Lepri L, et al. Alkylphenol polyethoxylate removal in a pilot-scale reed bed and phenotypic characterization of the aerobic heterotrophic community. Water Environ Res. 2006;78:754–63.Google Scholar
  10. 10.
    Ceśpedes R, Lacorte S, Ginebreda A, Barceló D. Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain). Environ Pollut. 2008;153:384–92.Google Scholar
  11. 11.
    Loos R, Hanke G, Umlauf G, Eisenreich S. LC–MS–MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters. Chemosphere. 2007;66:690–9.Google Scholar
  12. 12.
    Ahel M, McEvoy J, Giger W. Bioaccumulation of the lipophilic metabolites of nonionic surfactants in freshwater organisms. Environ Pollut. 1993;79:243–8.Google Scholar
  13. 13.
    Lee P, Lee W. In vivo estrogenic action of nonylphenol in immature female rats. Bull Environ Contam Toxicol. 1996;57:341–8.Google Scholar
  14. 14.
    Staples C, Mihaich E, Carbone J, Woodbrun K, Klecka G. A weight of evidence analysis of the chronic ecotoxicity of nonylphenol ethoxylates, nonylphenol ether carboxylates, and nonylphenol. Hum Ecol Risk Assess. 2004;10:999–1017.Google Scholar
  15. 15.
    Blackburn M, Waldock MJ. Concentrations of alkylphenols in rivers and estuaries in England and Wales. Water Res. 1995;29:1623–9.Google Scholar
  16. 16.
    Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 Amending Directive 2000/60/EC as regards priority substances in the field of water policy. 2013.Google Scholar
  17. 17.
    Perez-Fernandez V, Mainero Rocca L, Tomai P, Fanali S, Gentili A. Recent advancements and future trends in environmental analysis: sample preparation, liquid chromatography and mass spectrometry. Anal Chim Acta. 2017;983:9–41.Google Scholar
  18. 18.
    Grześkowiak T, Czarczyńska-Goślińska B, Zgoła-Grześkowiak A. Current approaches in sample preparation for trace analysis of selected endocrine-disrupting compounds: focus on polychlorinated biphenyls, alkylphenols, and parabens. Trends Anal Chem. 2016;75:209–26.Google Scholar
  19. 19.
    Jia Y, Su H, Wang Z, Wong Y, Chen X, Wang M, et al. Metal–organic framework@microporous organic network as adsorbent for solid-phase microextraction. Anal Chem. 2016;88:9364–7.Google Scholar
  20. 20.
    Gilart N, Miralles N, Marcé R, Borrull F, Fontanals N. Novel coatings for stir bar sorptive extraction to determine pharmaceuticals and personal care products in environmental waters by liquid chromatography and tandem mass spectrometry. Anal Chim Acta. 2013;774:51–60.Google Scholar
  21. 21.
    Benedé J, Chisvert A, Giokas D, Salvador A. Stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles–nylon 6 composite for the extraction of hydrophilic organic compounds in aqueous media. Anal Chim Acta. 2016;926:63–71.Google Scholar
  22. 22.
    Haunschmidt M, Klampfl C, Buchberger W, Hertsens R. Determination of organic UV filters in water by stir bar sorptive extraction and direct analysis in real-time mass spectrometry. Anal Bional Chem. 2010;397:269–75.Google Scholar
  23. 23.
    Salgueiro-González N, Concha-Graña E, Turnes-Carou I, Muniategui-Lorenzo S, López-Mahía P, Prada-Rodríguez D. Determination of alkylphenols and bisphenol A in seawater samples by dispersive liquid–liquid microextraction and liquid chromatography tandem mass spectrometry for compliance with environmental quality standards (Directive 2008/105/EC). J Chromatogr A. 2012;1223:1–8.Google Scholar
  24. 24.
    Zgola-Grześkowiak A. Dispersive liquid–liquid microextraction applied to isolation and concentration of alkylphenols and their short-chained ethoxylates in water samples. J Chromatogr A. 2010;1217:1761–6.Google Scholar
  25. 25.
    Rezaee M, Assadi Y, Milani Hosseini M, Aghaee E, Ahmadi F, Berijani S. Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A. 2006;1116:1–9.Google Scholar
  26. 26.
    Zhang Z, Ohiozebau E, Rhind S. Simultaneous extraction and clean-up of polybrominated diphenyl ethers and polychlorinated biphenyls from sheep liver tissue by selective pressurized liquid extraction and analysis by gas chromatography–mass spectrometry. J Chromatogr A. 2011;1218:1203–9.Google Scholar
  27. 27.
    Ferguson P, Iden C, Brownawell B. Analysis of nonylphenol and nonylphenol ethoxylates in environmental samples by mixed-mode high-performance liquid chromatography–electrospray mass spectrometry. J Chromatogr A. 2001;938:79–91.Google Scholar
  28. 28.
    Shang D, Ikonomou M, Macdonald R. Quantitative determination of nonylphenol polyethoxylate surfactants in marine sediment using normal-phase liquid chromatography–electrospray mass spectrometry. J Chromatogr A. 1999;849:467–82.Google Scholar
  29. 29.
    Schmitz-Afonso I, Loyo-Rosales J, Avilés M, Rattner B, Rice C. Determination of alkylphenol and alkylphenolethoxylates in biota by liquid chromatography with detection by tandem mass spectrometry and fluorescence spectroscopy. J Chromatogr A. 2003;1010:25–35.Google Scholar
  30. 30.
    Houde F, DeBlois C, Berryman D. Liquid chromatographic–tandem mass spectrometric determination of nonylphenol polyethoxylates and nonylphenol carboxylic acids in surface water. J Chromatogr A. 2002;961:245–56.Google Scholar
  31. 31.
    Takino M, Daishima S, Yamaguchi K. Determination of nonylphenol ethoxylate oligomers by liquid chromatography–electrospray mass spectrometry in river water and non-ionic surfactants. J Chromatogr A. 2000;904:65–72.Google Scholar
  32. 32.
    Cohen A, Klint K, Bøwadt S, Persson P, Jönsson J. Routine analysis of alcohol and nonylphenol polyethoxylates in wastewater and sludge using liquid chromatography–electrospray mass spectrometry. J Chromatogr A. 2001;927:103–10.Google Scholar
  33. 33.
    Sharma V, Anquandah G, Yngard R, Kim H, Fekete J, Bouzek K, et al. Nonylphenol, octylphenol, and bisphenol-A in the aquatic environment: a review on occurrence, fate, and treatment. J Environ Sci Health A. 2009;44:423–42.Google Scholar
  34. 34.
    López-García E, Mastroianni N, Postigo C, Barceló D, López de Alda M. A fully automated approach for the analysis of 37 psychoactive substances in raw wastewater based on on-line solid phase extraction-liquid chromatography-tandem mass spectrometry. J Chrom A. 2018;1576:80–9.Google Scholar

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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