High-resolution gas chromatography (HRGC) with electron-capture detection (ECD), nitrogen-phosphorus detection (NPD), flame ionization detection (FID) or with mass spectrometry-selected ion monitoring (MS-SIM) was used in the analysis of volatile carbonyl compounds. Eighteen carbonyl compounds that are typically produced during lipid peroxidation were derivatized quantitatively with pentafluorophenylhydrazine (PFPH) at room temperature, to afford their corresponding water-insoluble hydrazones. These derivatives were extracted into non-polar phases by means of either liquid-liquid extraction (LLE) (hexane) or solid-phase extraction (SPE) on 3 ml C18 octadecyl-bonded phase cartridges. Detection limits of 10(-14) and 10(-12) mol/ml per aldehyde were achieved with the ECD and MS-SIM systems, respectively. The effects of extraction conditions on sensitivity and recovery were determined by performing parallel HRGC-ECD and HRGC-MS-SIM analyses of pentafluorophenylhydrazones of the eighteen compounds under study. Recoveries of 51.4-78.9 +/- 1.2-4.5 and 80.9-98.3 +/- 1.0-3.5% were obtained with LLE and SPE, respectively. The method was applied to the analysis of the volatile carbonyl compounds in various heated vegetable oils (corn, palm or sunflower) and to the analysis of volatile aldehydes in human urine.