Evaluation of the quantitative analysis of a steroid sulphate using fast atom bombardment and tandem mass spectrometry

Dehydroepiandrosterone sulphate (DHAS) has been quantified in human blood serum by fast atom bombardment (FAB)/tandem mass spectrometry of immunoadsorption extracts. FAB of DHAS yielded abundant ions corresponding to the intact steroid sulphate; these were selected by a double-focusing mass spectrometer prior to collisionally activated decomposition in a quadrupole collision cell and mass analysis by a quadrupole mass filter. [HSO4]- (m/z 97) was the sole prominent daughter ion. For quadrupole mass filter was set to transmit m/z 97 and a narrow-range magnet scan yielded a spectrum of parents, including m/z 367 and 369, corresponding to DHAS and the (2H2)-analogue (used as internal standard), respectively. Serum concentrations by this procedure were in good agreement with data obtained by gas chromatographic/mass spectrometric analyses of DHA heptafluorobutyrate, formed by direct derivatization of the steroid sulphate.