A method for the airborne measurement of PAN, PPN, and MPAN

An aircraft‐based instrument for the measurement of peroxyacetic nitric anhydride (PAN) and related compounds peroxypropionic nitric anhydride (PPN), and peroxymethacrylic nitric anhydride (MPAN) is described. The instrument functions by direct injection of a small sample (2 ambient cm2) into a wide bore fused silica capillary gas chromatographic separation column with subsequent detection by electron capture. The efficiency of separation and early elution of water made possible a sampling frequency of once every 5 min. The selective destruction of PAN type compounds at 125°C in actual ambient samples showed that no interfering species were present. Calibration of the instrument was accomplished by the total odd‐nitrogen (NOy) measurement of air mixtures of high‐purity PANs. Inflight calibrations of PAN in either thermally decomposed ambient air or dry zero air showed that the sensitivity of the instrument to PAN was not affected by other matrix species such as carbon dioxide or water. The instrument response to PPN and MPAN relative to that of PAN was consistent (within 5%) over the span of several months. The instrument response to PAN was linear up to 3.5 ppbv and the slope of the response versus [PAN] indicated a relative standard deviation of 2% over the course of a 30‐day field study. The detection limits of the method for PAN and PPN were estimated to be 5 pptv (3s) based on the uncertainty of peak detection. The overall accuracy of the PAN measurement was estimated to be ±(5 pptv+15%) in one campaign and ±(5 pptv+20%) in others.