A comparison of calibration and measurement techniques for gas chromatographic determination of atmospheric peroxyacetyl nitrate (PAN)

A 24 day intercomparison study of peroxyacetyl nitrate (PAN) measurement was conducted in Egbert, Ontario, in February–March 1989. Two GC/ECD systems and one GC using a luminolchemiluminescence based detection device were involved. To separate the influence of calibration errors vs possible chromatographic interferences, a series of laboratory standards (gaseous PAN concentrations determined by either i.r. or by chemiluminescence) were exchanged. For all three GCs the results of analysis of standard samples were within ±25% of the standard concentration. For ambient air PAN measurements (concentrations ranging from 0.15 to 2 ppb), plots of each set of measurement data regressed against those of the other two techniques were obtained. Linear regression of the data from ambient air analysis for the two GC/ECD systems yielded a slope and intercept of 1.14±0.01 and −0.03±0.05, respectively (r = 0.995). The plot of the Luminol-based GC against the AES GC/ECD yielded a slope of 1.08±0.03 and an intercept of 0.08±0.24 (r = 0.864). The results demonstrated the reliability of the chemiluminescence calibration technique, and indicated that the luminol-based PAN measurement device can yield accurate and sensitive measurements of ambient PAN concentrations.