Dual-injection system with multiple injections for determining bidimensional retention indexes in comprehensive two-dimensional gas chromatography

A new instrumental approach for collection of retention index data in the first (1D) and second (2D) dimensions of a comprehensive two-dimensional (2D) gas chromatography (GCxGC) experiment has been developed. First-dimension indexes were determined under conventional linear programmed temperature conditions (Van den Dool indexes). To remove the effect that the short secondary column imposes on derived 1D indexes, as well as to avoid handling of pulsed GCxGC peaks, the proposed approach uses a flow splitter to divert part of the primary column flow to a supplementary detector to simultaneously generate a conventional 1D chromatogram, along with the GCxGC chromatogram. The critical 2D indexes (KovAts indexes) are based upon isovolatility curves of normal alkanes in 2D space, providing a reference scale against which to correlate each individual target peak throughout the entire GCxGC run. This requires the alkanes to bracket the analytes in order to allow retention interpolation. Exponential curves produced in the 2D separation space require a novel approach for delivery of alkane standards into the 2D column by using careful solvent-free solid-phase microextraction (SPME) sampling. Sequential introduction of alkane mixtures during GCxGC runs was performed by thermal desorption in a second injector which was directly coupled through a short transfer line to the entrance of the secondary column, just prior to the modulator so that they do not have to travel through the 1D column. Thus, each alkane mixture injection was quantitatively focused by the cryogenic trap, then launched at predetermined times onto the 2D column. The system permitted construction of an alkane retention map upon which bidimensional indexes of a 25-perfume ingredient mixture could be derived. Comparison of results with indexes determined in temperature-variable one-dimensional (1D) GC showed good correlation. Plotting of the separation power in the second dimension was possible by mapping Trennzahl values throughout the 2D space. The methodology was applied to the separation of a standard mixture composed of 25 analytes (very diverse in polarity and structure) suspected to be allergens in perfume samples. The method will allow straightforward determination of temperature-variable retention indexes of target analytes.