Baseline correction method for dynamic pressure gradient modulated comprehensive two-dimensional gas chromatography with flame ionization detection

•Baseline correction method was developed for dynamic pressure gradient modulation.•Background chromatogram normalization and subtraction is the key step.•Low boiling point alkane mixture was used for initial method development.•Method applicability was demonstrated using natural gas and gasoline samples.•The method has the most benefit for unretained analytes on the second dimension. A baseline correction method is developed for comprehensive two-dimensional (2D) chromatography (GC × GC) with flame-ionization detection (FID) using dynamic pressure gradient modulation (DPGM). The DPGM-GC × GC-FID utilized porous layer open tubular (PLOT) columns in both dimensions to focus on light hydrocarbon separations. Since DPGM is nominally a stop-flow modulation technique, a rhythmic baseline disturbance is observed in the FID signal that cycles with the modulation period (PM). This baseline disturbance needs to be corrected to optimize trace analysis. The baseline correction method has three steps: collection of a background “blank” chromatogram and multiplying it by an optimized normalization factor, subtraction of the normalization-optimized background chromatogram from a sample chromatogram, and application of Savitzky-Golay smoothing. An alkane standard solution, containing pentane, hexane and heptane was used for method development, producing linear calibration curves (r2 > 0.991) over a broad concentration range (7.8 ppm – 4000 ppm). Further, the limit-of-detection (LOD) and limit-of-quantification (LOQ) were determined for pentane (LOD = 2.5 ppm, LOQ = 8.2 ppm), hexane (LOD = 0.9 ppm, LOQ = 3.0 ppm), and heptane (LOD = 1.9 ppm, LOQ = 6.4 ppm). A natural gas sample separation illustrated method applicability, whereby the DPGM produced a signal enhancement (SE) of 30 for isopentane, where SE is defined as the height of the tallest 2D peak in the modulated chromatogram for the analyte divided by the height of the unmodulated 1D peak. The 30-fold SE resulted in about a 10-fold improvement in the signal-to-noise ratio (S/N) for isopentane. Additional versatility of the baseline correction method for more complicated samples was demonstrated for an unleaded gasoline sample, which enabled the detection (and visual appearance) of trace components.