1- and 2-photon ionization for online FAIMS-FTMS coupling allows new insights into the constitution of crude oils.

Photoionization techniques (APPI and APLI) are important for the mass spectrometric analysis of crude oils, given the mainly unpolar character of the sample. Ultrahigh resolving Fourier Transform mass spectrometry (FTMS) allows to distinguish between most isobaric compounds as well as to unambiguously determine the elemental compositions of the detected ions. Nevertheless, the complexity of crude oil makes its thorough analysis a difficult task. Besides discriminating effects that can be avoided and depth of information that can be gained by simplification of the sample prior to the MS analysis the presence of numerous isomeric compounds limits the amount of information that can be gained by mass spectrometry alone. Ion mobility spectrometry (IMS) has been shown to be a valuable tool for isomer separation and has also been employed for the analysis of crude oils using IMS-TOF MS. The application of an online FAIMS-FTMS coupling after photoionization for the analysis of crude oils is shown. With this setup the complementarity of data obtained from both APPI and APLI ionization is demonstrated. Online separation and individual detection of different hydrocarbon isomers is achieved.