Coupling of large volume injection with flow modulated two-dimensional gas chromatography

The coupling of large volume injection (LVI) with comprehensive two-dimensional gas chromatography (GC × GC) can be a powerful technique in the analysis of trace-level complex samples. The coupling of LVI and GC × GC using a cost efficiently operable pneumatic modulator based on capillary flow technology has been examined. The aim was to optimize the LVI parameters in the case of samples with compounds covering a wide boiling range. For the optimization of LVI 25 microliters of a solution containing 27 target compounds modelling the composition and the boiling range of diesel oils was used. The injection parameters were evaluated for peak shapes, reproducibility and peak volumes relative to peak volumes obtained using cold splitless injection. For all GC × GC experiments a non-polar first column (Rxi-5ms) and a polar second column (HP-INNOWax) were applied. Through extensive method optimization solvent vent proved to be an unsuitable technique for the injection of compounds covering a wide boiling range: at lower vent times peaks split, while higher vent times caused severe losses of highly volatile compounds. Therefore, a split-splitless LVI method was optimized. Injection speed, split vent time, splitless vent time and vent flow during split vent have been optimized. The developed method is suitable for the coupling of LVI with flow modulated GC × GC. Using the optimized split-splitless LVI parameters no peak distortion of the target compounds was observed. The relative peak volumes were between 60–120% for all compounds (80–120% for 13 compounds).