Atmospheric pressure single photon laser ionization (APSPLI) mass spectrometry using a 157 nm fluorine excimer laser for sensitive and selective detection of non- to semipolar hydrocarbons.

Atmospheric pressure single photon ionization (APSPLI) mass spectrometry utilizing a fluorine excimer laser (157 nm, 7.9 eV) is presented for the first time. For evaluation and optimization, polycyclic aromatic hydrocarbon (PAH) standard mixtures were used. The presented technique allowed for the selective ionization of semi- to nonpolar compounds in a single photon ionization process using VUV photons. Molecular radical cations were found as a base peak, whereas protonated species were almost absent. Although the ionization chamber is flushed by pure nitrogen, remaining oxygen and water traces caused unwanted oxidized ionization artifacts. Installation of water and oxygen filter cartridges significantly reduced the abundance of artifacts. For evaluating complex mixture analysis, APSPLI was applied to characterize a light crude oil. In addition to aromatic hydrocarbons, APSPLI allowed for the sensitive ionization of sulfur-containing aromatic constituents (PASH). A comparison of APSPLI to atmospheric pressure laser ionization (266 nm, 4.7 eV) revealed the additional compositional space accessible by the single photon process. APLI, conducted with UV radiation, is mainly restricted to PAH analysis. APSPLI overcomes this limitation, and PAH and PASH, which often occur simultaneously in complex mixtures, can be detected. This novel ionization concept is envisioned to have a high analytical potential further explored in the future