The two-dimensional (2D) data structure generated under a high resolution GC×GC system with a small number of samplings taken across the first dimension is evaluated for the purpose of the application of chemometric deconvolution methods. Chemometric techniques such as generalized rank annihilation method (GRAM) place high demands on the reproducibility of chromatographic experiments. For GRAM to be employed for GC×GC data interpretation, it is critical that the separation method provides data with a bilinear structure; the peak-shape and retention times on both columns must be reproducible. With a limited number of samplings across a 1D (first dimension) peak (e.g. four to six samplings) repeatability of the pattern of the modulated peaks (controlled by the modulation phase) becomes important in producing a bilinear data structure. Reproducibility of modulation phase can be affected by both reliability of the modulation period and reproducibility of the retention time of the peak on the first column (which arises from oven temperature and carrier flow rate stability). Evaluation of within-run and run-to-run retention time reproducibility (retention time uncertainty) on both columns, and modulation phase reproducibility using a modulated cryogenic system for a pair of overlapping components (fatty acid methyl esters) was undertaken. An investigation of the quality of data to permit quantification of each component by using GRAM deconvolution, was also conducted. Less than 4% run-to-run retention time uncertainty was obtained on column 1 and less than 9% run-to-run and within-run retention time uncertainty was obtained on column 2, where these R.S.D. measures are reported normalised to peak widths on each respective dimension. The R.S.D. of duplicate quantification results by GRAM ranged from 2 to 26% although the average quantification error using GRAM was less than 5%.
- Cryogenic modulation
- Fatty acid methyl esters