The net action of ruminal bacteria and endogenous bovine enzymes are responsible for cow's milk having the most complex fatty acid profiles among common foods. About 40 monounsaturated fatty acids below 1.5% w/w are known. Analysis of trace and ultratrace fatty acids is a challenge to the highest resolution chromatography even with prior fractionation. We employ solvent-mediated covalent adduct chemical ionization (CACI) tandem mass spectrometry (MS/MS) to enable rapid, unambiguous identification of unsaturated fatty acid methyl esters (FAME) at high sensitivity. Fifty-four monounsaturated fatty acids (C 10−24 ) were completely characterized, with the discovery of 15 novel fatty acids including nine at ultratrace levels 10−100 ppm, g/10 6 g fatty acids (lowest concentration 19:1n-6 (10 ± 11 ppm, w/w (0.001%, w/w))). Ultratrace monoenes were typically odd chain lengths and all analyzed in a single 20 min analysis. These data establish the abundance of 15 new monoene fatty acids in bovine milkfat and a strategy for rapid unambiguous analysis of ultratrace monounsaturated fatty acids.

Dairy and fermented foods are common sources of dietary branched-chain fatty acids (BCFA) of chain lengths C13–C18 serving a putative prebiotic role and a component of human integument. Few studies have reported on nonfermented plant-derived BCFA in human diets or cosmetics. A three-ion monitoring method was adapted to confirm branch position of ultratrace (<0.01%, w/w) BCFA. We identified chia as a new source of BCFA with C15–C35 chain lengths. Surprisingly, even-numbered very long-chain BCFA (VLC BCFA), anteiso-22:0, anteiso-24:0, and anteiso-26:0 were unequivocally identified in natural products for the first time. Plant-derived BCFA are predominantly anteiso, in contrast with similar iso and anteiso levels in ruminant and fermented foods. Chia seeds contain 0.4% BCFA, w/w of total fatty acids, or 32 mg BCFA in a food serving, surpassing other plant oils. Topical administration of chia seed oil containing VLC BCFA may have a role in skin and hair functionality.