Gas Chromatography Chemical Ionization Mass Spectrometry and Tandem Mass Spectrometry for Identification and Straightforward Quantification of Branched Chain Fatty Acids in Foods.

Fatty acid analysis of food lipids containing branched chain fatty acids (BCFAs) are complex because of unavoidable gas chromatography (GC) co-elution. We demonstrate a method for convenient quantitative GC coupled to novel solvent-mediated chemical ionization (CI) mass spectrometry (MS) that enables resolution of co-eluting peaks by mass. The relevant masses yield uniform responses for C14-20 normal fatty acids and BCFAs, eliminating the need for rare purified BCFA standards essential for unpredictable responses, as for electron ionization (EI). CI-tandem mass spectrometry analysis of MH+ yields fragments characteristic of the branch position. Application of the measurement to BCFAs in salami samples demonstrates consistent results for the novel method and EI-MS. A higher proportion of C17-18 BCFAs was found in beef compared to milkfat, possibly indicative of fatty acid elongation, endogenous in the beef animal. This method enables straightforward structure elucidation and quantification of food BCFAs and similar chain length normal fatty acids without purified standards.