Near-real-time measurement of trace volatile organic compounds from combustion processes using an on-line gas chromatograph

The US EPA's current regulatory approach for combustion and incineration sources considers the use of real-time continuous emission monitors (CEMs) for particulate, metals, and organic compounds to monitor source emissions. Currently, the CEM technologies to support this approach have not been thoroughly developed and/or demonstrated. The EPA's Air Pollution Prevention and Control Division has developed a near-real-time volatile organic compound (VOC) CEM, using an on-line gas chromatograph (OLGC), capable of measuring over 20 VOCs at concentrations typically present in well-operated combustion systems. The OLGC system consists of a sample delivery system, a sample concentrator, and a GC equipped with both flame ionization and electron capture detectors. Application of the OLGC system was initially demonstrated through participation in the 1995 US EPA/DOE CEM demonstration program. Additional work has improved system performance, including increased automation and improved calibration technique. During pilot-scale incineration testing, measurement performance was examined in detail through comparisons to various CEM performance criteria. Specifically, calibration error, calibration drift error, and system bias were examined as a function of full scale (absolute error) and gas concentration (relative error). Although OLGC measurement performance was not able to meet standard EPA CEM measurement performance criteria, measurement performance was encouraging. The system demonstrated the ability to perform hourly trace level VOC measurements (0–100 ppbv) for as many as 23 different VOCs with boiling points ranging from −23.7 to 180.5 °C at a known level of measurement performance. This system is a suitable alternative to VOC reference method measurements which may be performed only intermittently.