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 accuracy of ESI Fourier transform mass spectrometry further allows unequivocal identification of molecular formulas within PAH mixtures.