Trichloroethylene (TCE) is a chlorinated liquid that is commonly used for metal degreasing, household and industrial dry cleaning, and in paints and glues. Tetrachloroethylene, also known as perchloroethylene (PCE), is an excellent solvent for organic materials. PCE is volatile, highly stable, non-flammable and widely used in dry cleaning. A new method has been developed for measuring TCE and PCE in ambient air in real-time. Based upon the chemical fingerprinting and concentration levels, the method was able to isolate the source of the emissions to the responsible facility. Real-time monitoring was accomplished by utilizing a low pressure chemical ionization source (LPCI) interfaced to a tandem mass spectrometer (TAGA). Monitoring the response of specific parent/daughter ion pairs, the TAGA was used to measure concentrations of TCE and PCE. By optimizing various TAGA parameters, detection limits (DL) as low as 0.5 μg/m³ was achieved for TCE and PCE. Unlike methods using cartridge sampling and GC/MS analysis, this new method provides a real time measurement for a wide range of TCE and PCE concentrations. This unique method was applied in 2000 and 2002 to measure TCE emitted from a manufacturer of stainless steel tubing in Eastern Ontario. The maximum half-hour average concentration of TCE measured downwind of the facility was 1300 μg/m³ and the maximum instantaneous level was measured at 115,000 μg/m³. The information collected by the TAGA unit was used by the Standard Development Branch of Ontario Ministry of the Environment to adopt the half-hour Point of Impingement (POI) standard of TCE to be 36 μg/m³ in 2010. This method successfully identified and simultaneously measured TCE and PCE during a 2011 air monitoring survey of a hazardous waste disposal and treatment facility in Southern Ontario.