Determination of non-ionic and anionic surfactants in industrial products by separation on a weak ion-exchanger, derivatization and liquid chromatography

• The joint determination of non-ionic and anionic surfactant classes is described.
• Ethoxylated alcohols, alkylether sulfates and alkylbenzenesulfonates are included.
• A WAX cartridge is used to obtain a non-ionic and an anionic fraction.
• The advantages of using WAX instead of SAX are highlighted.
• Application to laundry and industrial cleaners and toiletries is demonstrated.

A method for the determination of priority surfactants, including fatty alcohol ethoxylates (FAE), alkylether sulfates (AES) and linear alkylbenzene sulfonates (LAS) is described. The samples were diluted with 50% methanol at pH 4 prior to solid-phase extraction on a weak anionic exchanger (WAX). The AES and LAS surfactant classes were retained, whereas the non-ionic components, including most FAE oligomers were eluted. After washing the WAX cartridge to remove cations, the remaining hydrophobic FAE oligomers were eluted using hot 80% methanol at pH 4 (at ca. 50 °C). These two eluates were combined to constitute the non-ionic fraction. Then, AES and LAS were eluted using 80% MeOH with 3 M NH3 followed by 95% methanol with 0.75 M NH3. The two eluates obtained in basic media were combined to constitute the anionic fraction. The solvents were evaporated, the residues were dissolved in 1,4-dioxane, and esterification of the alcohols and transesterification of AES with phthalic anhydride was performed. Separation of the derivatized oligomers was achieved by gradient elution on a C8 column with acetonitrile/water in the presence of 0.1% acetic acid and 0.1 M NaClO4. The chromatogram of the non-ionic fraction showed the peaks of the resolved FAE oligomers. The chromatogram of the anionic fraction showed the peaks of the LAS homologues well resolved from those of the AES oligomers. The method was applied to laundry and industrial cleaners, shampoos and a shower gel.