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Headspace sampling is compared with purge-and-trap techniques for the gas chromatographic (GC) analysis of volatile pollutants in water. An objective comparison of the two sample introduction techniques was made by using the same GC, column, and detectors for identical analyses run first by purge and trap and then by headspace. Using optimized headspace conditions described in this article, this technique was as sensitive as the US Environmental Protection Agency purge-and-trap methods for the analysis of volatile pollutants in water. The precision for 24 sequential headspace injections was better than that for purgeand-trap analyses. The relative advantages and disadvantages for these two sampling methods are also discussed. Includes 24 references, tables, figures.