Highly volatile organic compounds with low water solubility are extracted (purged) from a 5-mL sample by bubbling an inert gas through the aqueous sample. Purged sample components are trapped in a tube containing a suitable sorbent material. When purging is complete, the sorbent tube is heated and backflushed with an inert gas to desorb trapped sample components onto a gas chromatography (GC) column. The gas chromatograph is temperature programmed to separate the method analytes which are then detected with a photoionization detector. A second chromatographic column is described that can be used to help confirm GC identifications or resolve coeluting compounds. Analyses may be performed by gas chromatography/mass spectrometry (GC/MS) according to Method 524.1 or Method 524.2.