Analytical and Bioanalytical Chemistry

, Volume 411, Issue 13, pp 2759–2765 | Cite as

Characterization and analysis of non-ionic surfactants by supercritical fluid chromatography combined with ion mobility spectrometry-mass spectrometry

  • Qiang MaEmail author
  • Yun Zhang
  • Junfeng Zhai
  • Xi Chen
  • Zhenxia Du
  • Wentao Li
  • Hua BaiEmail author


Comprehensive separation and analysis of non-ionic surfactants have been conducted by coupling supercritical fluid chromatography (SFC) with ion mobility spectrometry-mass spectrometry (IMS-MS). Representative non-ionic surfactants were investigated, including alkylphenol ethoxylates (APEOs), e.g., octylphenol ethoxylates (OPEOs) and fatty alcohol ethoxylates (FAEs), e.g., lauryl alcohol ethoxylates (LAEs). A sub-2-μm high-density diol column was used for chromatographic separation by the first-dimensional SFC due to the differences in ethoxy chain prior to electrospray ionization (ESI). Maintaining the fidelity of pre-ionization separation in the first dimension, the introduction of IMS provided additional post-ionization resolution by broadly fractionating the oligometric ethoxymers based on their size and electric charge within 13.78 ms. Distinguishable series of singly and multiply charged non-ionic species could be clearly observed. The millisecond timescale ion mobility separation perfectly fits the elution time of a chromatographic peak, while effectively feeding components into the fast-scanning time-of-flight (TOF) mass analyzer for characterization and analysis. The orthogonality of the developed separation and analysis system was evaluated, revealing a correlation coefficient and peak spreading angle of 0.2729 and 74.16° for the studied OPEOs and 0.1962 and 78.69° for LAEs. Significant enhancement in peak capacity was achieved for the developed SFC-IMS-MS system with the actual peak capacity measured to be approximately 41 and 160 times higher than that of the dimensions of SFC and IMS, respectively, when used alone.

Graphical abstract


Supercritical fluid chromatography Ion mobility spectrometry-mass spectrometry Non-ionic surfactants Alkylphenol ethoxylates Fatty alcohol ethoxylates 



This work was financially supported by the National Key R&D Program of China (2016YFF0203702).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

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  1. 1.
    Acir I-H, Guenther K. Endocrine-disrupting metabolites of alkylphenol ethoxylates—a critical review of analytical methods, environmental occurrences, toxicity, and regulation. Sci Total Environ. 2018;635:1530–46. Scholar
  2. 2.
    Jardak K, Drogui P, Daghrir R. Surfactants in aquatic and terrestrial environment: occurrence, behavior, and treatment processes. Environ Sci Pollut Res. 2016;23(4):3195–216. Scholar
  3. 3.
    Plata MR, Contento AM, Ríos Á. Analytical characterization of alcohol-ethoxylate substances by instrumental separation techniques. TrAC Trends Anal Chem. 2011;30(7):1018–34. Scholar
  4. 4.
    Gatidou G, Thomaidis NS, Stasinakis AS, Lekkas TD. Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography–mass spectrometry. J Chromatogr A. 2007;1138(1-2):32–41. Scholar
  5. 5.
    Loyo-Rosales JE, Schmitz-Afonso I, Rice CP, Torrents A. Analysis of octyl- and nonylphenol and their ethoxylates in water and sediments by liquid chromatography/tandem mass spectrometry. Anal Chem. 2003;75(18):4811–7. Scholar
  6. 6.
    Ferguson PL, Iden CR, Brownawell BJ. Analysis of alkylphenol ethoxylate metabolites in the aquatic environment using liquid chromatography–electrospray mass spectrometry. Anal Chem. 2000;72(18):4322–30. Scholar
  7. 7.
    Zembrzuska J, Budnik I, Lukaszewski Z. Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry. J Sep Sci. 2014;37(13):1694–702. Scholar
  8. 8.
    Lara-Martín PA, Gómez-Parra A, González-Mazo E. Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study. Environ Pollut. 2008;156(1):36–45. Scholar
  9. 9.
    González S, Petrović M, Radetic M, Jovancic P, Ilic V, Barceló D. Characterization and quantitative analysis of surfactants in textile wastewater by liquid chromatography/quadrupole-time-of-flight mass spectrometry. Rapid Commun Mass Spectrom. 2008;22(10):1445–54. Scholar
  10. 10.
    Luo X, Zhang L, Niu Z, Ye X, Tang Z, Xia S. Liquid chromatography coupled to quadrupole-Orbitrap high resolution mass spectrometry based method for target analysis and suspect screening of non-ionic surfactants in textiles. J Chromatogr A. 2017;1530:80–9. Scholar
  11. 11.
    Berger TA. Supercritical fluid chromatography: overview. Reference module in chemistry, molecular sciences and chemical engineering. Elsevier; 2013.Google Scholar
  12. 12.
    Glenne E, Öhlén K, Leek H, Klarqvist M, Samuelsson J, Fornstedt T. A closer study of methanol adsorption and its impact on solute retentions in supercritical fluid chromatography. J Chromatogr A. 2016;1442:129–39. Scholar
  13. 13.
    Grand-Guillaume Perrenoud A, Veuthey J-L, Guillarme D. The use of columns packed with sub-2 μm particles in supercritical fluid chromatography. TrAC Trends Anal Chem. 2014;63:44–54. Scholar
  14. 14.
    Takahashi K. Polymer analysis by supercritical fluid chromatography. J Biosci Bioeng. 2013;116(2):133–40. Scholar
  15. 15.
    Auerbach RH, Dost K, Jones DC, Davidson G. Supercritical fluid extraction and chromatography of non-ionic surfactants combined with FTIR, APCI-MS and FID detection. Analyst. 1999;124(10):1501–5.
  16. 16.
    Pan J, Ji Y, Du Z, Zhang J. Rapid characterization of commercial polysorbate 80 by ultra-high performance supercritical fluid chromatography combined with quadrupole time-of-flight mass spectrometry. J Chromatogr A. 2016;1465:190–6. Scholar
  17. 17.
    Jiang Z-J, Cao X-L, Li H, Zhang C, Abd El-Aty AM, Jin F, Shao H, Jin M-J, Wang S-S, She Y-X, Wang J. Fast determination of alkylphenol ethoxylates in leafy vegetables using a modified quick, easy, cheap, effective, rugged, and safe method and ultra-high performance supercritical fluid chromatography–tandem mass spectrometry. J Chromatogr A. 2017;1525:161–72.
  18. 18.
    Bijttebier S, D’Hondt E, Noten B, Hermans N, Apers S, Voorspoels S. Ultra high performance liquid chromatography versus high performance liquid chromatography: stationary phase selectivity for generic carotenoid screening. J Chromatogr A. 2014;1332:46–56. Scholar
  19. 19.
    Wilkins CL, Trimpin S. (Ed.). (2011). Ion mobility spectrometry-mass spectrometry. Boca Raton: CRC Press., 2013.Google Scholar
  20. 20.
    Solak Erdem N, Alawani N, Wesdemiotis C. Characterization of polysorbate 85, a nonionic surfactant, by liquid chromatography vs. ion mobility separation coupled with tandem mass spectrometry. Anal Chim Acta. 2014;808:83–93. Scholar
  21. 21.
    Ma Q, Xi G-C, Wang C, Bai H, Zhang Q, Xi H-W, Wang Z-M, Guo L-H. Comprehensive two-dimensional separation for the analysis of alkylphenol ethoxylates employing hydrophilic interaction chromatography coupled with ion mobility-mass spectrometry. Int J Mass Spectrom. 2012;315:31–9.
  22. 22.
    Ma Q, Ma W, Chen X, Wang Z, Bai H, Zhang L, Li W, Wang C, Li X. Comprehensive analysis of fatty alcohol ethoxylates by ultra high pressure hydrophilic interaction chromatography coupled with ion mobility spectrometry mass spectrometry using a custom-designed sub-2 μm column. J Sep Sci. 2015;38(12):2182–91.
  23. 23.
    Åsberg D, Enmark M, Samuelsson J, Fornstedt T. Evaluation of co-solvent fraction, pressure and temperature effects in analytical and preparative supercritical fluid chromatography. J Chromatogr A. 2014;1374:254–60. Scholar
  24. 24.
    West C, Khater S, Lesellier E. Characterization and use of hydrophilic interaction liquid chromatography type stationary phases in supercritical fluid chromatography. J Chromatogr A. 2012;1250:182–95. Scholar
  25. 25.
    Ashraf-Khorassani M, Taylor LT, Seest E. Screening strategies for achiral supercritical fluid chromatography employing hydrophilic interaction liquid chromatography-like parameters. J Chromatogr A. 2012;1229:237–48. Scholar
  26. 26.
    Vajda P, Guiochon G. Modifier adsorption in supercritical fluid chromatography onto silica surface. J Chromatogr A. 2013;1305:293–9. Scholar
  27. 27.
    West C, Lesellier E. Characterisation of stationary phases in subcritical fluid chromatography with the solvation parameter model: III. Polar stationary phases. J Chromatogr A 2006;1110(1):200–213. doi:
  28. 28.
    Berger TA. Characterization of a 2.6 μm Kinetex porous shell hydrophilic interaction liquid chromatography column in supercritical fluid chromatography with a comparison to 3 μm totally porous silica. J Chromatogr A. 2011;1218(28):4559–68. Scholar
  29. 29.
    Emmett MR, Kazazic S, Marshall AG, Chen W, Shi SD, Bolaños B, Greig MJ. Supercritical fluid chromatography reduction of hydrogen/deuterium back exchange in solution-phase hydrogen/deuterium exchange with mass spectrometric analysis. Anal Chem. 2006;78(19):7058–60.
  30. 30.
    de la Puente ML, Soto-Yarritu PL, Anta C. Placing supercritical fluid chromatography one step ahead of reversed-phase high performance liquid chromatography in the achiral purification arena: a hydrophilic interaction chromatography cross-linked diol chemistry as a new generic stationary phase. J Chromatogr A. 2012;1250:172–81. Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Chinese Academy of Inspection and QuarantineBeijingChina
  2. 2.College of ScienceBeijing University of Chemical TechnologyBeijingChina
  3. 3.Waters CorporationShanghaiChina

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