Dynamic pressure gradient modulation for comprehensive two-dimensional gas chromatography with time-of-flight mass...

Dynamic pressure gradient modulation (DPGM) is investigated for comprehensive two-dimensional gas chromatography (GC × GC) with time-of-flight mass spectrometry (TOFMS) detection. With DPGM, a commercial pneumatic "pulse" valve is opened to introduce a suitably high auxiliary gas pressure at a T-junction connecting the first dimension (¹D) and second dimension (²D) columns during the modulation period (P_M), temporarily stopping the ¹D flow. The valve is then closed for the duration of a pulse width (p_w) to "re-inject" temporally focused ¹D eluate onto the ²D column for separation. This flow modulation technique is observed to be compatible with TOFMS detection using a ²D flow rate of 4 ml/min for the separation of a 90-component test mixture. A 25 min separation window using a P_M = 1 s and p_w = 200 ms for full modulation (and 100% duty cycle) provided an average ¹W_b = 4.5 s and ²W_b = 130 ms for a 2D peak capacity of n_c,2D = 2700 (100 peaks per min). The detector response enhancement factor (DREF) serves as a metric for the enhanced sensitivity of the modulated relative to the unmodulated ¹D peaks, with DREFs ranging between 10 and 20 and about a 5-fold improvement in signal-to-noise ratio (S/N). The bilinear "quality" of the GC × GC data is studied using the chemometric method parallel factor analysis (PARAFAC). Since PARAFAC requires sufficiently trilinear data, the reproducibility of the ²D peak shape for a given analyte is confirmed using lack-of-fit (LOF) and percent variation (R²) metrics. The limit-of-detection (LOD) for the representative analyte hexadecane is determined using PARAFAC, providing an LOD of 0.7 ppb (±0.03 ppb) for three replicates. Seven heavily overlapped analytes are also fully resolved by PARAFAC down to the part-per-million (ppm) concentration level, producing reproducible spectra with a majority of spectral match values (MV) over 800 (RSD ≤ 7.1%). This study provides promising results for DPGM as a flow modulation technique compatible with GC × GC-TOFMS, providing high sensitivity data suitable for chemometric analysis.