Development of primary reference gas mixtures of 18 volatile organic compounds in hazardous air pollutants (5 nmol/mol level) and their analytical methods

Volatile organic compounds (VOCs) in hazardous air pollutants (HAPs) have been regulated by the Air Pollution Control Act (1978) and their atmospheric concentrations have been monitored in 39 monitor sites in Korea. However, measurement standards of volatile organic compounds (VOCs) in HAPs at ambient levels have not been established in Korea. Primary reference gas mixtures (measurement standards) at ambient levels are required for accurately monitoring atmospheric VOCs in HAPs and managing their emissions. In this study, primary reference gas mixtures (PRMs) at 5 nmol/mol were developed in order to establish primary national standards of VOCs in HAPs at ambient levels. Primary reference gas mixtures (PRMs) were prepared in pressurized aluminum cylinders with special internal surface treatment using gravimetric method. Analytical methods using gas chromatography-flame ionization detector (GC-FID) coupled with a cryogenic preconcentrator were also developed to verify the consistency of gravimetrically prepared HAP VOCs PRMs. Three different columns installed in the GC-FID were evaluated and compared for the retention times and separation of eighteen target components in a chromatogram. Results show that the HAP VOCs PRMs at 5 nmol/mol were consistent within a relative expanded uncertainty (k=2) of less than 3 % except acrylonitrile (less than 6 %) and the 18 VOCs were stable for 1 year within their associated uncertainties.