A recently introduced rapid-scanning quadrupole mass spectrometer (qMS) with an electron-capture negative ion (ECNI) option, the Perkin-Elmer Clarus 500, was tested as a detector for comprehensive two-dimensional gas chromatography (GC × GC). The parameters influencing the data acquisition rate in the scan mode, such as scan time and inter-scan delay, and in the selected ion monitoring mode, such as dwell time and inter-channel delay, were evaluated. In the scan mode, good-quality mass spectra covering a range of 300 Da can be obtained at an acquisition rate of 23 Hz; in selected ion monitoring, an acquisition rate of 90 Hz can be achieved when monitoring a single ion. Compared with electron ionisation, the use of electron-capture negative ionisation causes no extra peak broadening. As applications, mixtures of polychlorinated n-alkanes (PCAs), polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo- p-dioxins (PCDDs) and dibenzofurans (PCDFs) were analysed. The separation of PCAs based on their number of chlorine substituents was confirmed for the first time by using GC × GC–ECNI qMS in the scan mode and a significantly improved limit of detection was achieved for BDEs (10–150 fg injected) and CDD/Fs (10–700 fg injected) in the selected ion monitoring mode.
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