Comprehensive two-dimensional gas chromatography can be viewed as a traditional gas chromatography with a sophisticated "elution-resolved" flame ionization detector (GC/FID) or a detector with separation capability. The concept of multidimensional chromatography can be extended to other detectors that also have separation capability, such as ultraviolet, infrared, and mass spectrometer. Mass spectrometry, combined with gas chromatography, GC/MS, has been a powerful separation/identification device for many years. However, if one applies the multidimensional separation concept to this combination with a nonfragmentation ionization method, GC/MS not only can be used as a separation/identification tool, but also a two (multiple) dimensional separation device, GCxMS. In this study, a two-dimensional separation (GCxMS) study of diesel composition is demonstrated and compared with the GCxGC technique. The major advantage of GCxMS is the compound class separation. The compound groups within a compound class are also well-separated on the basis of their parent masses. Because of the exact mass operation, the specific element containing compound distribution can also be generated through the extraction of specific mass groups. For qualitative analysis, GCxMS is a technique where one experiment can generate a wide range of information. GCxMS may also perform quantitative analysis when appropriate response factors for various compound groups are available. From GCxGC to GCxMS, the power of two (multiple) dimensional separation has just started exposing its advantages for complex mixture analysis. To achieve multiple dimensional separation in different forms, many improvements remain to be made. The challenge now is to combine/accommodate two or more different techniques to solve a specific complex separation problem. The GCxMS experience has pushed this effort one step ahead toward complete application of this new concept in the analysis of complex mixtures.

Nitrogen-containing compounds in diesel fuel have been speciated by comprehensive two-dimensional gas chromatography with nitrogen chemiluminescence detector (GC x GC-NCD). The speciation of nitrogen-containing compounds in diesel is difficult because of low concentration and complexity. The advantages of GC x GC are improved resolution and enhanced sensitivity. GC x GC-NCD can achieve the type and class separation of nitrogen-containing compounds with an appropriate separation column combination. Diesel contains both neutral (indoles and carbazoles) and basic (pyridines and quinolines) nitrogen-containing compounds. Relative concentrations of each class as well as each carbon number family can be quantified by integrating their peak volumes. This study demonstrates the capability of GC x GC-NCD for speciation of nitrogen-containing compound classes.

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Sulfur-containing compounds in diesel have been speciated by comprehensive two-dimensional gas chromatography (GCxGC) with a sulfur chemiluminescence detector (SCD). The advantages of GCxGC technique are higher resolution and greater sensitivity. GCxGC-SCD can achieve the class separation of sulfur-containing compounds with an appropriate separation column combination. The major classes of sulfur-containing compounds in diesel are benzothiophenes and dibenzothiophenes. Relative concentration of each class as well as each carbon number family can be quantitated by the summation of the integrated areas corresponding to the individual group(s) in the GCxGC space. In practical applications, GCxGC-SCD can be used to characterize different diesels and to reflect desulfurization process efficiency. In this study, GCxGC-SCD has demonstrated its value in speciation of sulfur-containing compounds classes, which is difficult to accomplish by any other single technique.

Detailed compositional analyses of sedimentary organic matter can provide information on its biotic input, environment of deposition, and level of thermal maturation. Pyrolysis-gas chromatography (py-GC), often coupled with a mass spectrometer (py-GC/MS), is one technique used to provide this information. New developments in comprehensive two-dimensional gas chromatography (GC x GC or 2D-GC), coupled with pyrolysis (py-GC x GC), offer the prospect of providing more complete and quantitative compositional information of complex organic solids, such as kerogen and coals. This study will describe applications of pyrolysis-GC x GC to the characterization of petroleum source rocks using flame ionization detector (FID) and sulfur chemiluminescence detector (SCD). In the hydrocarbon analysis by FID, paraffins, naphthenes, and aromatics form distinct two-dimensional separated groups. In the analysis with SCD, sulfur-containing compounds can be distinguished as different classes, such as mercaptans, sulfides, thiophenes, benzothiophenes, and dibenzothiophenes. Single components or summed bands of homologous components can be analyzed qualitatively and quantitatively. With these detailed molecular fingerprints, the relations between kerogen composition and its biotic input, environment of deposition, and thermal maturation may be better understood.