Free radical-mediated inflammatory processes account for a great portion of morbidity and mortality in critically ill patients. The purpose of this study was to determine two plasma peroxidation markers and three volatile markers related to lipid peroxidation, metabolic activity and cholesterol metabolism, and to explore relationships between the different markers and patients' clinical status. Substances were analyzed in whole blood and in exhaled air in patients with head injury, acute respiratory distress syndrome (ARDS) and in those being at risk of developing ARDS. These results were compared with the baseline measurements in healthy individuals. Additionally, patients were assessed according to their inflammatory status. Concentrations of malondialdehyde and thiobarbituric acid-reactive substances in plasma as well as pentane concentrations in breath increased with increasing inflammatory status. Although these compounds are generated through peroxidation of fatty acids, concentrations of these markers were significantly different in patient groups. Isoprene concentrations were lowest in the ARDS group. Acetone concentrations were not different between patient groups. We conclude that for the assessment of lipid peroxidation and other inflammatory reactions a set of parameters has to be defined. More detailed insights into inflammatory processes can be obtained when the volatile markers and the serum markers are considered together.