The Department of Energy (DOE), Morgantown Energy Technology Center (METC), is involved in the characterization of organic components present in the process and by-product streams generated by coal gasification in DOE/METC's 42-inch stirred fixed-bed gasifier. The primary objective of this characterization program is the generation of basic data on the total organic loadings in various process and by-product streams and the distribution of organic compounds at critical points throughout the cleanup system. The samples collected are initially separated into solid, water-soluble, and tar and oil fractions. Organic solvent extracts of the tars and oils are then subjected to capillary column gas chromatography and gas chromatography/mass spectrometry analysis. Because of the number of components typically present in the tar and oil extracts, identification of every compound is very time-consuming. In response to this, a rapid gas chromatographic identification procedure to analyze organic compounds in tar and oil extracts using a relative retention index (RRI) system has been developed by Argonne National Laboratory (ANL). This system and accompanying software has been used in the analysis and identification of samples from the DOE/METC gasifier. The results, which are processed into a convenient from by the software, can be used to build a data base to allow further analyses, such as the correlation of the composition of process streams with gasifier operating conditions. 9 refs., 4 figs., 5 tabs.