Mass spectrometry/mass spectrometry: capabilities and applications to fuel-related materials

The expanding capabilities of mass spectrometry/mass spectrometry (m.s.-m.s.) in mixture analysis and its applications to fuel-related materials are illustrated. High and low collision energy m.s.-m.s. data obtained on reverse geometry and triple quadrupole spectrometers are given for coal-derived liquid (SRC II) and diesel particulate samples. The direct analysis capability of the m.s.-m.s. methodology and its limitations are illustrated for the identification of an aliphatic carboxylic acid in diesel paniculate. The selective ionization techniques of ammonia chemical ionization and negative chemical ionization are shown to be particularly useful in enhancing the specificity of m.s.-m.s. characterizations. Negative chemical ionization is used to confirm the presence of hydroxybenzoic acid in a diesel particulate sample. Combined laser desorption-chemical ionization is also demonstrated to be an effective ionization technique in m.s.-m.s. analysis. A variant of m.s.-m.s., in which selected anions fragment with charge inversion to give fragment cations, is also employed in the analysis of SRC II and used to identify thioaryl moieties. Functional group screening by an alternative m.s.—m.s. scan procedure, neutral loss scanning, is demonstrated for phenols in SRC II. A scan for all parent ions of a selected daughter ion provides a screening procedure for rapidly identifying all compounds of a given structural type in a complex mixture. The dependence of m.s.-m.s. spectra on collision energy and pressure is shown to add further detail to m.s.—m.s. analysis. The development of a library of m.s.—m.s. spectra of reference compounds to be used for the identification of individual constituents in fuel-related materials is described.