Journal of Surfactants and Detergents

, Volume 7, Issue 2, pp 195–202 | Cite as

Characterization of alcohol ethoxylates as alcohol ethoxy sulfate derivatives by liquid chromatography-Mass spectrometry

  • Giorgio Cassani
  • Claudio Pratesi
  • Lorella Faccetti
  • Stefano Pravettoni
  • Giancarlo Nucci
  • Nunzio Andriollo
  • Luigi Valtorta
  • Lee Matheson
Article

Abstract

The characterization of alcohol ethoxylates (AE) to determine ethylene oxide (EO) adduct distribution has been studied in our laboratory for many years by using high-performance liquid chromatography-mass spectrometry (LC-MS). This paper describes the LC-MS approach being used to analyze both nonderivatized and derivatized AE. We conclude that the best way to determine EO adduct distribution is by first converting the AE to alcohol ethoxy sulfates (AES) and then by using LC-MS with electrospray ionization in the negative ion mode. A convenient laboratory technique for converting small-scale samples of AE to AES has been discovered and is reported herein. Several examples of EO adduct distribution determined by this method are presented for both linear and isomeric AE samples.

Key Words

AE AES alcohol ethoxy sulfates alcohol ethoxylates alcohol ether sulfates analysis anionic surfactants LC-MS mass spectrometry nonionic surfactants 

Abbreviations

AE

alcohol ethoxylates

AES

alcohol ethoxy (or ethoxylated or ether) sulfates

APGI

atmospheric pressure chemical ionization

AS

alcohol sulfates

ESI

electrospray ionization

EO

ethylene oxide

GC-MS

gas chromatography-mass spectrometry

HPLC

high-performance liquid chromatography

LC-MS

liquid chromatography-mass spectrometry

LOD

limit(s) of detection

SO3-DMF

sulfur trioxide dimethylformamide

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References

  1. 1.
    Pratesi, C.R., L. Faccetti, and G. Cassani, Anionic Surfactant Composition by GC-Mass Spectrometry, Riv. Ital. Sostanze Grasse 78:273 (2000).Google Scholar
  2. 2.
    Cohen, L., F. Soto, M.S. Luna, C.R. Pratesi, G. Cassani, and L. Faccetti, Analysis of Sulfoxylated Methyl Esters: Sulfonic Acid Composition and Isomer Identification, J. Surfact. Deterg. 6:151 (2003).Google Scholar
  3. 3.
    Rasmussen, H.T., A.M. Pinto, M.W. DeMouth, P. Touretzky, and B.P. McPherson, High Temperature Gas Chromatography of Trimethylsilyl Derivatives of Alcohol Ethoxylates and Ethoxysulfates, J. High Resolul. Chromatogr. 17:593 (1994).CrossRefGoogle Scholar
  4. 4.
    Asmussen, C., and H.-J. Stan, Determination of Nonionic Surfactants of the Alcohol Polyethoxylate Type by Means of High Temperature Gas Chromatography and Atomic Emission Detection, J. High Resolut. Chromatogr. 21:597 (1998).CrossRefGoogle Scholar
  5. 5.
    Geissler, P.R., Quantitative Analysis of Ethoxylated Alcohols by Supercritical Fluid Chromatography, Anal. Chem. 66:685 (1989).Google Scholar
  6. 6.
    Kalinoski, H.T., and A. Jensen, Characterization of Nonionic Surfctants Using Supercritical Fluid Chromatography and Carbon-13 Nuclear Magnetic Resonance Spectroscopy, J. Am. Oil Chem. Soc. 66:1171 (1989).Google Scholar
  7. 7.
    Johnson, A.E., P.R. Geissler, and L.D. Talley, Determination of Relative Ethoxylation Rate Constants from Supercritical Fluid Chromatographic Analysis of Ethoxylated Alcohols, Anal. Chem. 67:123 (1990).Google Scholar
  8. 8.
    Silver, A.H., and H.T. Kalinoski, Comparison of High-Temperature Gas Chromatography and Carbon Dioxide Supercritical Fluid Chromatography for the Analysis of Alcohol Ethoxylates, J. Am. Oil Chem. Soc. 69:599 (1992).Google Scholar
  9. 9.
    Stan, H.-J., T. Heberer, and P. Billian, Determination of Alcohol Ethoxylates in Drinking Water, Vom Wasser 90:93 (1998).Google Scholar
  10. 10.
    Cavalli, L., A. Gellera, G. Cassani, M. Lazzrin, C. Maraschin, and G. Nucci, Analysis of Non-ionics and Alcohol Ethoxylates. Application to Confirmatory Test Effluents, Riv. Delle Sostanze Grasse 70:447 (1993).Google Scholar
  11. 11.
    Allen, M.C., and D.E. Linder, Ethylene Oxide Oligomer Distribution in Nonionic Surfactants via High-Performance Liquid Chromatography, J. Am. Oil Chem. Soc. 60:950 (1981).Google Scholar
  12. 12.
    Aserin, A., M. Frenkel, and N. Garti, HPLC Analysis of Nonionic Surfactants. Part IV. Polyoxyethylene Fatty Alcohols, J. Am. Oil Chem. Soc. 61:805 (1984).Google Scholar
  13. 13.
    Sato, T., Y. Saito, and I. Anazawa, Polyoxyethylene Oligomer Distribution of Non-ionic Surfactans J. Am. Oil Chem. Soc. 65:996 (1988).Google Scholar
  14. 14.
    Murphy, R.E., and M.R. Schure, and J.P. Foley, One-and Two-Dimensional Chromatographic Analysis of Alcohol Ethoxylates, Anal. Chem. 70:4353 (1998).CrossRefGoogle Scholar
  15. 15.
    Marcomini, A., G. Pojana, C. Carrer, L. Cavalli, G. Cassani, and M. Lazzarin, Aerobic Biodegradation of Monobranched Aliphatic Alcohol Polyethoxylates, Environ. Toxicol. Chem. 19:555 (2000).CrossRefGoogle Scholar
  16. 16.
    Kiewie, A.T., J.M.D. Van Der Stee, and J.R. Parsons, Trace Analysis of Ethoxylated Non-ionic Surfactants in Samples of Influent and Effluent of Sewage Treatment Plants by High-Performance Liquid Chromatography, Anal. Chem. 67:4409 (1995).CrossRefGoogle Scholar
  17. 17.
    Zanette, M., A. Marcomini, E. Marchiori, and R. Samperi, High-Performance Liquid Chromatographic-Fluorescence Determination of Aliphatic alcohol Polyethoxylates and Polyethyleneglycols in Aqueous Samples, J. Chromatgr. A 756:159 (1996).CrossRefGoogle Scholar
  18. 18.
    Bachus, H., and H.-J. Stan, High-Performance Liquid Chromatographi-IV Analysis of Aliphatic Alcohol Ethoxylates and Their Corresponding Sulfates by Esterification with 2-Furoyl-Chloride, Tenside Surfact. Deterg. 40:10 (2003).Google Scholar
  19. 19.
    Cretier, G., C. Podevin, and J.L. Rocca, Analysis of Aliphatic Alcohol Ethoxylates in Terms of Alkyl and Ethylene Oxide Chain Lengths by Reversed-Phase Liquid Chromatography with Evaporative Light-Scattering Detection, J. Chromatogr. A 874:305 (2000).CrossRefGoogle Scholar
  20. 20.
    Schlotterbeck, G., H. Pasch, and K. Albert, Online HPLC-1H NMR Coupling for the Analysis of Fatty Alcohol Ethoxylates, Polymer Bull. (Berlin) 8:673 (1997).CrossRefGoogle Scholar
  21. 21.
    Heinig, K., C. Vogt, and G. Wermer, Separation of Nonionic Surfactants by Capillary Electrophoresis and High-Performance Chromatography, Anal. Chem. 70:1885 (1998).CrossRefGoogle Scholar
  22. 22.
    Trathnigg, B., C. Rappel, R. Hodl, and S. Fraydl, Molecular Characterization of Ethoxylates by Complementary Chromatographic Techniques. Evaluation of Efficiency and Reliability, Tenside Surfact. Deterg. 40:3 (2003).Google Scholar
  23. 23.
    Jandera, P., M. Holcapek, and G. Theodoridis, Investigation of Chromatographic Behaviour of Ethoxylated Alcohol Surfactants in Normal-Phase and Reversed-Phase Systems Using High-Performance Liquid Chromatography-Mass Spectrometry, J. Chromatogr. A 813:299 (1998).CrossRefGoogle Scholar
  24. 24.
    Huang, S.K., and M.H. Rood, The Analysis of Alkyl-Capped Alcohol Ethoxylates and Alcohol Ethoxycarboxylates from Alcohol Ethoxylates by Atmospheric Pressure Chemical Ionization Mass Spectrometry, Rapid Commun. Mass Spectrom. 13:1152 (1999).CrossRefGoogle Scholar
  25. 25.
    Wang, X.-C., and Y. Jin, Analysis of Carbon Number and Ethylene Oxide Number Distribution in Alcohol Ethoxylates by HPLC Electrospray Ionization Mass Spectrometry, Sepu 18:332 (2000).Google Scholar
  26. 26.
    Spiker, R., B. Menzebach, and K. Kube, Analysis of Surfactants in Formulations by Mass Spectrometry, Riv. Ital. Sostanze Grasse 78:241 (2001).Google Scholar
  27. 27.
    Di Corcia A., C. Crescenzi, A. Marcomini, and R. Samperi, Liquid Chromatography-Electrospray-Mass Spectrometry as a Valuable Tool for Characterizing Biodegradation Intermediates of Branched Alcohol Ethoxylate Surfactants, Environ. Sci. Technol. 32:711 (1998).CrossRefGoogle Scholar
  28. 28.
    Cuzzola, A., A. Raffaelli, A. Saba, and P. Salvadori, Identification and Characterization of Fenton Oxidation Products of Surfactants by Electrospray Mass Spectrometry and Solid Phase Microextraction Gas Chromatography/Mass Spectrometry. 3. Polyethoxylated Fatty Alcohols and Nonylphenols, Rapid Commun. Mass Spectrom 15:1198 (2001)CrossRefGoogle Scholar
  29. 29.
    Fornara, D., S. Lago, and V. Porta, Characterization and Determination of Anionic and Non-ionic Surfactants by Liquid Chromatography-Mass Spectrometry, in Proceeding of the 5th World Surfactants Congress (Firenze, Italy, May 29–June 2, 2000), Comité Européen des Agents de Surface et leurs Intérmediaires Organiques, Brussels, Belgium, 2000, p. 472.Google Scholar
  30. 30.
    Schröder H.F., Tracing of Surfactants in the Biological Wastewater Treatment Process and the Identification of Their Metabolites by Flow Injection-Mass Spectrometry and Liquid Chromatography-Mass Spectrometry and Tandem Mass Spectrometry, J. Chromatogr. 926:127 (2001).CrossRefGoogle Scholar
  31. 31.
    Battersby, N.S., A.J. Sherren, R.N. Bumpus, R. Eagle, and I.K. Molade, The Fate of Linear Alcohol Ethoxylates During Activated Sludge Sewage Treatment, Chemosphere 45:109 (2001).CrossRefGoogle Scholar
  32. 32.
    Bruno, F., R. Curini, A. Di Corcia, I. Fochi, M. Nazzari and R. Samperi, Determination of Surfactants and Some of Their Metabolites in Untreated and Anaerobically Digested Sewage Sludge by Subcritical Water Extraction Followed by Liquid Chromatography-Mass Spectrometry, Environ. Sci. Technol. 36:4156 (2002).CrossRefGoogle Scholar
  33. 33.
    Schröder, H.F., Surfactants: Non-biodegradable, Significant Pollutants in Sewage Treatment Plant Effluents. Separation, Identification, and Quantification by Liquid Chromatography, Flow-Injection Analysis-Mass Spectrometry, and Tandem Mass Spectrometry, J. Chromatogr. 647:219 (1993).CrossRefGoogle Scholar
  34. 34.
    Evans, K.A., S.T. Dubev, L. Kravetz, I. Dzidic, J. Gumulka, R. Mueller, and J.R. Stork, Quantitative Determination of Linear Primary Alcohol Ethoxylate Surfactants in Environmental Samples by Thermospray LC/MS, Anal. Chem. 66:699 (1994).CrossRefGoogle Scholar
  35. 35.
    Crescenzi, C., A. Di Corcia, R. Samperi, and A. Marcomini, Determination of Nonionic Polyethoxylate Surfactants in Environmental Waters by Liquid Chromatography/Electrospray Mass Spectrometry, Anal. Chem., 67:1797 (1995).CrossRefGoogle Scholar
  36. 36.
    Cassani, G., M. Comber, A. Guarini, J. Lux, M. Hetheridge, and R. Wolf, Determination of Alcohol Ethoxylates in Environmental Samples by Thermospray Liquid Chromatography-Mass Spectrometry, in Proceedings of the 4th World Surfactants Congress (Barcelona, Spain, June 3–7, 1996), Comité Européen des Agents de Surface et leurs Intérmediaires Organiques, Brussels, Belgium, 1996, Vol. 4, p. 436.Google Scholar
  37. 37.
    Evans, K.A., S.T. Dubey, L. Kravetz, S.W. Evetts, I. Dzidic, and C.C. Dooyema, Quantitation of Alcohol Ethoxylate Surfactants in Environmental Samples by Electrospray Mass Spectrometry, J. Am. Oil Chem. Soc. 74:765 (1997).Google Scholar
  38. 38.
    Di Corcia, A., C. Crescenzi, A. Marcomini, and R. Samperi, Liquid Chromatography-Electrospray-Mass Spectrometry as a Valuabler Tool for Characterizing Biodegradation Intermediates of Branched Alcohol Ethoxylate Surfactants, Environ. Sci. Technol. 32:711 (1998).CrossRefGoogle Scholar
  39. 39.
    Castillo, M., M.C. Alonso, J. Riu, and D. Barcelo, Identification of Polar, Ionic, and Highly Soluble Organic Pollutants in Untreated Industrial Wastewaters, Environ. Sci. Technol. 33:1300 (1999).CrossRefGoogle Scholar
  40. 40.
    Matthijs, E., M.S. Holt, A. Kiewit, and G.B.J. Rijs, Environmental Monitoring for Linear Alkylbenzene Sulfonate, Alcohol Ethoxylate, Alcohol Ethoxysulfate, and Soap, Environ. Sci. Toxicol. 18:2634 (1999).CrossRefGoogle Scholar
  41. 41.
    Dunphy, J.C., D.G. Pessler, S.W. Morrall, K.A. Evans, D.A. Robaugh, G. Fujimoto, and A. Negahban, Derivatization LC/MS for the Simultaneous Determination of Fatty Alcohol Ethoxylate Surfactants in Water and Wastewater Samples, Environ. Sci. Technol. 35:1223 (2001).CrossRefGoogle Scholar
  42. 42.
    Petrovic, M., A.R. Fernandez-Alba, F. Borrull, R.M. Marce, E.G. Mazo, and D. Barcelo, Occurrence and Distribution of Nonionic Surfactants, Their Degradation Products, and Linear Alkylbenzene Sulfonates in Coastal Waters and Sediments in Spain, Environ. Toxicol. Chem. 2:37 (2002).CrossRefGoogle Scholar
  43. 43.
    Cohen, A., K. Klint, S. Bøwadt, P. Persson, and J.A. Jönsson, Rotitine Analysis of Alcohol and Nonylphenol Polyethoxylates in Waste Water and Sludge Using Liquid Chromatography-Electrospray Mass Spectrometry, J. Chromatogr. A 927:103 (2001).CrossRefGoogle Scholar
  44. 44.
    Krogh, K.A., K.V. Vejrup, B. Mogensen, and B. Halling-Sorensen, Liquid Chromatography Mass Spectrometry Method to Determine Alcohol Ethoxylates and Alkylamine Ethoxylates in Soil Interstitial Water, Ground Water, and Surface Water Samples, J. Chromatogr. A 957:45 (2002).CrossRefGoogle Scholar
  45. 45.
    Bartsch, H., M. Strassner, and U. Hintze, Characterization and Identification of Ethoxylated Surfactants by Matrix Assisted Laser Desorption/Ionization Mass Spectrometry, Tenside Surfact. Deterg. 35:94 (1998).Google Scholar

Copyright information

© AOCS Press 2004

Authors and Affiliations

  • Giorgio Cassani
    • 1
  • Claudio Pratesi
    • 1
  • Lorella Faccetti
    • 1
  • Stefano Pravettoni
    • 1
  • Giancarlo Nucci
    • 1
  • Nunzio Andriollo
    • 1
  • Luigi Valtorta
    • 1
  • Lee Matheson
    • 2
  1. 1.Sasol Italy S.p.A. Research & TechnologyPaderno Dugnano(MI)Italy
  2. 2.Sasol North America Inc.Austin

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