Techniques and application in comprehensive multidimensional gas chromatography – mass spectrometry

In contrast to the well-known comprehensive two-dimensional gas chromatography (GC×GC) method, it is possible to define comprehensive multidimensional gas chromatography. ‘Comprehensiveness’ relates to analysis of the whole sample. Two-dimensional and multidimensional here refer to the use of at least two separation stages for analysis, however comprehensive 2DGC now appears to be reserved for the GC×GC method. This may be differentiated from comprehensive MDGC (CMDGC) simply by the analysis time assigned to the second (2D) column, although there does not appear to be a specific definition that relates to this analysis time parameter. A number of different implementation protocols for comprehensive MDGC are described here, that may involve either a single, or multiple, injection(s). In all cases, independent retention must be achieved on each dimension to ensure the probability of enhanced separation. An original application of a crude oil sample is presented to illustrate development of the MDGC approach that incorporates two Deans switches (DS) and a cryogenic trapping approach, performed using a sequential heart-cut (H/C) event method incremented by 0.5 min for each injection; a total of 40 injections is used to analyse the total sample. The higher peak capacity and consequently greater resolution on the long 2D column is illustrated, compared with that expected for conventional GC×GC, with tentative identification in order to classify chemical classes. Incorporating an approach to acquiring retention indices may be implemented, although its utility for petroleum hydrocarbons is limited. Structured groupings of different chemical classes, as exemplified by mono and diaromatics for the crude oil sample, were noted.