Characterization of polychlorinated n-alkanes using comprehensive two-dimensional gas chromatography–electron-capture negative ionisation time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography with electron-capture negative ionization time-of-flight mass spectrometry (GC × GC–ECNI-TOF-MS) is used to study the composition and characteristics of short-, medium- and long-chain polychlorinated n-alkane (PCA) mixtures. Distinct ordered structures, which enable the highlighting and interpretation of group and sub-group separations are observed when using a DB-1 × 007-65HT column combination. The analysis of a number of, mutually rather different, technical mixtures and 35 individual standard compounds provides information on the role of chlorine substitution (number of substituents as well as their position), the contribution of carbon versus chlorine atoms to analyte volatility, i.e. GC × GC behaviour, and the influence of the chain length of the carbon skeleton. Two dust samples are analyzed to illustrate the practical usefulness of the proposed procedure.