Gas Chromatography/Multiphoton Ionization/Mass Spectrometry of Polychlorinated Dibenzofurans Using Nanosecond and Femtosecond Lasers

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOF-MS) using a femtosecond laser source has been developed and applied to analysis of an authentic sample containing five polychlorinated dibenzofurans (PCDFs). The ionization efficiency was substantially improved for compounds such as tetrachlorinated dibenzofuran (tetraCDF) and pentachlorinated dibenzofuran (pentaCDF) using a femtosecond laser, instead of a nanosecond laser currently used for this purpose. The relatively poor efficiencies in nanosecond ionization can be attributed to the short lifetimes of the singlet excited states that are efficiently relaxed to triplet levels by intersystem crossing. The detection limits for pentaCDF isomers, i.e., 1,2,3,8,9-pentaCDF (non-toxic) and 1,2,3,7,8-pentaCDF (toxic), were determined to be ca. 100 pg, when the femtosecond laser was employed. The present method has the potential for use in the detection and determination of toxic PCDD/Fs in exhaust gas from an incinerator, because of the high inherent selectivity of GC and the high sensitivity of MPI/TOF-MS.