Accurate
and comprehensive identification of residual glycerides
in biodiesel is an important part of fuel characterization due to
the impact of glycerides on the fuel physicochemical properties. However,
analysis of bound glycerol in biodiesel samples faces challenges due
to lack of readily available standards of structurally complex glyceride
species in nontraditional biodiesel feedstocks and a risk of misannotation
in the presence of impurities in gas chromatographic separations.
Here, we evaluate methane and isobutane chemical ionization–single
quadrupole mass spectrometry combined with high-temperature gas chromatography
separations for mapping monoacylglycerols, diacylglycerols, and triacylglycerols
in biodiesel. Unlike electron impact ionization, which produces mostly
in-source fragments, isobutane chemical ionization spectra of tetramethylsilyl-derivatized
monoacylglycerols and diacylglycerols are dominated by molecular ions
and M-SiO(CH3)3
+ ions, which provide
important diagnostic information. We demonstrate the utility of isobutane
chemical ionization in identifying structurally complex glycerolipid
standards as well as species in biodiesel samples from different plant
and animal feedstocks.