Parallel dual secondary column-dual detection: A further way of enhancing the informative potential of two-dimensional comprehensive gas chromatography

• Improved gas linear velocities in both chromatographic dimensions.
• Positive effects on overall system orthogonality and resolution.
• Higher secondary column loading capacity.
• Internal cross-validation of quantitation accuracy.

Comprehensive two-dimensional gas chromatography (GC × GC) coupled with Mass Spectrometry (MS) is one of today's most powerful analytical platforms for detailed analysis of medium-to-high complexity samples. The column set usually consists of a long, conventional-inner-diameter first dimension (1D) (typically 15–30 m long, 0.32–0.25 mm dc), and a short, narrow-bore second dimension (2D) column (typically 0.5–2 m, 0.1 mm dc) where separation is run in a few seconds. However, when thermal modulation is used, since the columns of a set are coupled in series, a flow mismatch occurs between the two dimensions, making it impossible to operate simultaneously at optimized flow conditions. Further, short narrow-bore capillaries can easily be overloaded, because of their lower loadability, limiting the effectiveness of 2D separation.In this study, improved gas linear velocities in both chromatographic dimensions were achieved by coupling the 1D column with two parallel 2D columns, having identical inner diameter, stationary phase chemistry, and film thickness. In turn, these were connected to two detectors: a fast quadrupole Mass Spectrometer (MS) and a Flame Ionization Detector (FID). Different configurations were tested and performances compared to a conventional set-up; experimental results on two model mixtures (n-alkanes and fourteen medium-to-high polarity volatiles of interest in the flavor and fragrance field) and on the essential oil of Artemisia umbelliformis Lam., show the system provides consistent results, in terms of analyte identification (reliability of spectra and MS matching) and quantitation, also affording an internal cross-validation of quantitation accuracy.