Evaluation of conditions of comprehensive two-dimensional gas chromatography that yield a near-theoretical maximum in peak capacity gain

The peak capacity gain (Gn) of a GC × GC system is the ratio of the system peak capacity to that of an optimized one-dimensional GC analysis lasting the same time and providing the same detection limit. A near-theoretical maximum in Gn has been experimentally demonstrated in GC × GC-TOF based on a 60 m × 0.25 mm primary column. It was found that Gn was close to 9 compared to the theoretical maximum of about 11 for this system. A six-sigma peak capacity of 4500 was obtained during an 80 min heating ramp from 50 °C to 320 °C. Using peak deconvolution, 2242 individual peaks were determined in a Las Vegas runoff water sample. This is the first definitive experimental demonstration known to us of an order-of-magnitude Gn. The key factors enabling this gain were: relatively sharp (about 20 ms at half height) reinjection pulses into the secondary column, relatively long (60 m) primary column, the same diameters in primary and secondary columns, relatively low retention factor at the end of the secondary analysis (k ≅ 5 instead of 15, optimal for ideal conditions), optimum flow rate in both columns, and helium (rather than hydrogen) used as the carrier gas. The latter, while making the analysis 65% longer than if using H2, was a better match to the reinjection bandwidth and cycle time.