Precursor ion approach for simultaneous determination of nonethoxylated and ethoxylated alkylsulfate surfactants

We present a new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for simultaneous determination of sodium lauryl sulfate and sodium laureth sulfate homologues in the range of alkyl chain length C₁₂-C₁₆ with 0-5 ethoxy groups. The method is based on scanning the precursor ions fragmenting to m/z 80 and 97 (Precursor Ion Scanning mode), which makes it specific for species with easily cleavable sulfate groups. By monitoring fragmentation of thus discovered quasi-molecular ions we were able to unequivocally identify all sulfate species present in complex mixtures of alkyl and alkyl-ether sulfates with molecular weight ranging from 200 to 600 m/z. Because of the intrinsic sulfate-sensitivity, the presented method can be also applied to non-sodium salts of alkyl- and alkyl-ether sulfates (e.g. ammonium, mono- or triethanolamine, etc.), which are often used by cosmetic manufacturers to justify the misleading SLS- and SLES-free claims (where SLS and SLES refer to sodium lauryl sulfate and sodium laureth sulfate, respectively). The use of reversed phase liquid chromatography (RPLC) column with C4 instead of C18 shortened significantly the overall analysis time and allowed us to use a semiquantitative method (based on single standard for Quantitative Analysis of Multi-component System, QAMS) to determine several SLS and SLES homologues in one run with the limit of quantification (LOQ) = 0.4 µg/mL and of detection (LOD) in the range 0.12-0.97 µg/mL. The method was successfully applied to 17 commercially available cosmetic/household products allowing verification of their manufacturers' declarations.