Electrospray ionization Fourier transform mass spectrometry of polycyclic aromatic hydrocarbons using silver(I)-mediated ionization

Here, a methodology employing doped Ag(I) salt as an in situ cationization reagent for efficient ionization of nonpolar molecules within a conventional electrospray ionization source is described. The effectiveness of Ag(I)-mediated ionization is demonstrated using ESI Fourier transform mass spectrometry for the rapid detection and identification of priority pollutant polyaromatic hydrocarbon (PAH) species. In contrast to earlier coordination ESI-MS reports employing silver salts, argentated species are not typically observed for PAH species. Instead, oxidation of the PAH occurs to produce only the [PAH]+· odd-electron molecular parent ion, simplifying spectral analysis. In addition, the method demonstrates linear quantitative performance. The Ag(I) reagent provides quantifiable PAHs (not ordinarily amenable to ESI-MS) from 64 ppb, and suggests the immediate potential for sampling and on-line monitoring of complex, real world, and otherwise intractable environmental samples. Finally, the high mass accurac...