A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy

• Published in: Atmospheric Measurement Techniques
• Main Authors: Tokarek, T. W., Huo, J. A., Odame-Ankrah, C. A., Hammoud, D., Taha, Y. M., Osthoff, H. D.
• Format: Article in Journal/Newspaper
• Language: English
• Published: Copernicus Publications 2014
• Subjects: article; Verlagsveröffentlichung; Fort McMurray
• Online Access: https://doi.org/10.5194/amt-7-3263-2014; https://noa.gwlb.de/receive/cop_mods_00018862; https://noa.gwlb.de/servlets/MCRFileNodeServlet/cop_derivate_00018817/amt-7-3263-2014.pdf; https://amt.copernicus.org/articles/7/3263/2014/amt-7-3263-2014.pdf

The peroxycarboxylic nitric anhydrides (PANs, molecular formula: RC(O)O2NO2) can readily be observed by gas chromatography (PAN-GC) coupled to electron capture detection. Calibration of a PAN-GC remains a challenge, because the response factors differ for each of the PANs, and because their synthesis in sufficiently high purity is non-trivial, in particular for PANs containing unsaturated side chains. In this manuscript, a PAN-GC and its calibration using diffusion standards, whose output was quantified by blue diode laser thermal dissociation cavity ring-down spectroscopy (TD-CRDS), are described. The PAN-GC peak areas correlated linearly with total peroxy nitrate (ΣPN) mixing ratios measured by TD-CRDS (r > 0.96). Accurate determination of response factors required the concentrations of PAN impurities in the synthetic standards to be subtracted from ΣPN. The PAN-GC and its TD-CRDS calibration method were deployed during ambient air measurement campaigns in Abbotsford, BC, from 20 July to 5 August 2012, and during the Fort McMurray Oil Sands Strategic Investigation of Local Sources (FOSSILS) campaign at the AMS13 ground site in Fort McKay, AB, from 10 August to 5 September 2013. The PAN-GC limits of detection for PAN, PPN, and MPAN during FOSSILS were 1, 2, and 3 pptv, respectively. For the Abbotsford data set, the PAN-GC mixing ratios were compared, and agreed with those determined in parallel by thermal dissociation chemical ionization mass spectrometry (TD-CIMS). Advantages and disadvantages of the PAN measurement techniques used in this work and the utility of TD-CRDS as a PAN-GC calibration method are discussed.