Development of a Standardized Protocol for the Classification of Column Sets in Comprehensive Two-Dimensional Gas Chromatography

One-dimensional gas chromatography (1D-GC) stationary phases are generally classified according to their relative polarity into non-polar, semi-polar, and polar columns. In comprehensive two-dimensional gas chromatography (GC×GC), it is the polarity difference between the two tandem-assembled stationary phases that determines the selectivity of the column ensemble. This polarity difference is called orthogonality, and GC×GC column sets can be broadly categorized into four groups based on the direction of the serial coupling between the primary and secondary columns. A significant portion of the GC×GC column sets in use today are operated in forward-orthogonality mode, which means that the secondary column is more polar than the primary column. A growing number of reported GC×GC applications operate in reversed-orthogonality configurations, where the secondary column is less polar than the primary column. Very few examples exist of non-orthogonal column sets because of the fact that there is limited additional selectivity that the secondary column can offer over the separation that has already been achieved in the primary column when the two phases are either identical or close in polarity. The fourth group of GC×GC column sets, called hybrid orthogonality, involves the coupling of stationary phases with peculiar selectivity differences that manifest themselves in the bi-dimensional separation plots. In this work, we are presenting a normalized approach to GC×GC column set characterization that is based on the use of a reference mixture of standards called the Century Mix. The Century Mix contains 100 chemical probes of different functionalities that span a reasonable range of volatilities and polarities to capture the selectivity profile of any GC×GC column set. The Century Mix also contains important chemical probes that are used for 1D-GC column characterization (such as the Grob mix and the Rohrschneider/McReynolds compounds) to make some connections between the 1D-GC building block columns and the GC×GC column sets. We finally also outline some other important metrics of comparison that should be taken into consideration to assess the overall performance of a GC×GC system.