Characterization of polar substituted polycyclic aromatic compounds using high-resolution gas chromatography/mass spectrometry negative ion chemical ionization and positive and negative ion thermospray liquid chromatography/mass spectrometry.

The sensitivity and selectivity of high-resolution gas chromatography/mass spectrometry in the negative ion chemical ionization mode with methane as reagent gas was evaluated for the characterization of polar substituted polycyclic aromatic compounds (PAC). The fragmentation patterns were affected by the nature of the substituent for polar substituted nitro-PAC that showed detection limits of 50 pg at full-scan acquisition. This technique has been applied to the characterization of polar high-performance liquid chromatographic fractions of diesel exhaust particulate (NBS Standard Reference Material 1650) and enabled the identification of 20 PAC of different chemical classes. Among them, hydroxynitro-, dinitro- and nitrosubstituted secondary amines were identified for the first time in diesel exhaust particulate. In addition, 'filament-on' thermospray (TSP) liquid chromatography/mass spectrometry (LC/MS) with positive and negative ions have been used for the characterization of similar polar compounds such as 2-nitroquinoline, 1,8-naphthalic anhydride, naphthalene sulphonic acid and 1,2-hydroxynitronaphthalene. LC analyses were performed on a reversed-phase system using either acetonitrile-water or methanol-water with 0.1 M ammonium acetate and 1% acetic acid as eluent. With negative ion TSP LC/MS a four- to fivefold loss in sensitivity was observed for naphthalene sulphonic acid compared with nitrohydroxy-PAC, that showed a minimum detectable amount of 50 ng in the reconstructed ion chromatogram.