[Post-print] Direct quantitation and characterization of fatty acids in salmon tissue by condensed phase membrane introduction mass spectrometry (CP-MIMS) using a modified donor phase

Abstract

Existing mass spectrometric methods for the analysis of fatty acids often require derivatization, chromatographic separations and/or extensive sample preparation. Direct mass spectrometry strategies can avoid these requirements, but may also suffer from poor quantitation and/or lack of sensitivity. Condensed phase – membrane introduction mass spectrometry (CP-MIMS) provides direct quantitative measurements of analytes in complex samples with little or no sample preparation. CP-MIMS uses a semipermeable membrane to transfer neutral, hydrophobic compounds from real-world samples to a mass spectrometer. The results presented utilize aqueous/organic sample solvent (donor) mixtures to allow for the sensitive (pptr) detection of a range of fatty acids. The relative sensitivity across a homologous series of fatty acids is observed to change, favouring short or long chain fatty acids, depending on the amount of miscible cosolvent added to the donor phase. Further, lithium acetate added online via the acceptor phase was used in tandem mass spectrometry experiments to determine the location of double bonds in polyunsaturated fatty acids (PUFAs). The method was applied to direct measurements and structural determinations for selected PUFAs in salmon tissue samples. Standard addition was employed to quantify the amount of PUFAs in a variety of salmon samples, yielding 0.27 – 0.42 and 0.40 – 0.84 w/w % for eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), respectively, for Sockeye and Chinook salmon, in good agreement with the literature. This work presents, to our knowledge, the first use of CP-MIMS for the direct analysis of fatty acids in oily foodstuff samples.