We used real-time breath measurement technology to investigate the suitability of some volatile organic compounds (VOCs) as breath biomarkers for active and passive smoking and to measure actual exposures and resulting breath concentrations for persons exposed to tobacco smoke. Experiments were conducted with five smoker/nonsmoker pairs. The target VOCs included benzene, 1,3-butadiene, and the cigarette smoke biomarker 2,5-dimethylfuran. This study includes what we believe to be the first measurements of 1,3-butadiene in smokers' and nonsmokers' breath. The 1,3-butadiene and 2,5-dimethylfuran peak levels in the smokers' breath were similar (360 and 376 microg/m(3), respectively); the average benzene peak level was 522 microg/m(3). We found higher peak values of the target chemicals and shorter residence times in the body than previously reported, probably because of the improved time resolution made possible by the continuous breath measurement method. The real-time breath analyzer also showed the presence of the chemicals after exposure in the breath of the nonsmokers, but at greatly reduced levels. Single breath samples collected in evacuated canisters and analyzed independently with gas chromatography/mass spectrometry confirmed the presence of the target compounds in the postexposure breath of the nonsmokers but indicated that there was some contamination of the breath analyzer measurements. This was likely caused by desorption of organics from condensed tar in the analyzer tubing and on the quartz fiber filter used to remove particles. We used the decay data from the smokers to estimate residence times for the target chemicals. A two-compartment exponential model generally gave a better fit to the experimental decay data from the smokers than a single-compartment model. Residence times for benzene, 1,3-butadiene, and 2,5-dimethylfuran ranged from 0.5 (1,3-butadiene) to 0.9 min (benzene) for tau1 and were essentially constant (14 min) for tau2. These findings will be useful in models of environmental tobacco smoke exposure and risk.