The ubiquitous detection of perfluorooctane sulfonate (PFOS) in humans and animals has produced a need for sensitive and compound-specific analytical methods to determine the environmental distribution of fluorinated organic contaminants. A suite of potential PFOS precursors (sulfonamides) and fluorotelomer alcohols (FTOHs) were separated by gas chromatography and detected by chemical ionization mass spectrometry (GC/CI-MS). Full-scan spectra were collected in both positive and negative chemical ionization (PCI and NCI, respectively) mode to determine retention time windows and fragmentation patterns. In selected ion monitoring (SIM) mode, instrumental detection limits ranged from 0.2 to 20 pg for individual analytes, depending on ionization mode. PCI mode was preferred for routine analysis because of the simple mass spectra produced, typified by the presence of a major molecular ion [M + H]+. High-volume air samplers collected gaseous and particle-bound fluoroorganics on composite media consisting of XAD-2, polyurethane foam (PUF), and quartz-fiber filters. The combined collection efficiency for individual analytes was 87 to 136% in breakthrough experiments. Application of the method to the analysis of ambient air from urban and rural sites confirmed the presence of six novel fluorinated atmospheric contaminants at picogram per meter3 concentrations. Low concentrations of fluoroorganics were consistently detected in blanks (<4 pg m(-3)); however, this did not prevent confirmation or quantification of environmental concentrations.