of this journal, Ryan and Marriott introduced comprehensive two-dimensional gas chromatography (GC×GC) [1], and presented an overview of the principles of the technique, the stateof-the-art of the instrumentation and the perspectives. In the present paper we will elaborate on this theme and focus attention on the potential and practicality of the technique.Since its introduction in the early nineties, it has generally become recognised -as is evident from an impressive body of published papers -that GC×GC is a versatile technique that can be applied to essentially all GC-amenable, complex samples and analyte classes. The three main advantages of GC×GC are: (i) a very high separation capacity, (ii) improved analyte detectability and (iii) generation of structured chromatograms.
SeparationAs a result of the orthogonality (i.e. independent separation mechanisms; see [2]) of the two separating dimensionsusually a 20-30-m non-polar first column and a short 0.5-1-m polar/selective second column -to which all constituents of a sample are subjected, the separation power of the GC×GC system is roughly equal to the product of the separation powers of the individual columns. In other words, in a 2D separation plane far more compounds can be (baseline) resolved than in a conventional 1D chromatographic trace. This is convincingly demonstrated in the literature for a variety of (very) complex samples. What should be emphasised here is that, next to the enhanced separation of the analytes from each other, another major advantage is the separation of these analytes from a large part of the interfering background. These major benefits of GC×GC are discussed in a recent review [2]. This paper also reports all published fields of application, such as petroleum products [3,4], flavours and fragrances in food [5, 6], polyhalogenated micro-contaminants in fish [7], pesticides in fruit and vegetables [8], FAMEs [9], geochemical samples, and air, biological and industrial samples. A selected number of examples are presented in Table 1. The most impressive example is the analysis of cigarette smoke [10], which yields no less than 30,000 peaks.
DetectionThe second advantage, improved analyte detectability, is due to the focusing effect of the (cryogenic) modulator. Since the separation of each modulated fraction on the short second column has to be completed before the next fraction is injected, the second-dimension separation takes only a few seconds. To prevent peak broadening, the modulator focuses the first-column eluate fractions into very narrow pulses (typical width, ca. 10 ms) prior to injection on the second column. Because of the mass conservation in all, except valve-based, modulators, this results in peak amplitudes that are, typically, enhanced 20-150-fold. However, since such narrow peaks demand a very high data acquisition rate of up to 200 Hz, with which noise is generally present more prominently, the considerable peak enhancement results in a much more modest, i.e. 5-10-fold, improvement of the limits of detection (LODs...