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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union

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Atmos. Meas. Tech., 7, 3263-3283, 2014
https://doi.org/10.5194/amt-7-3263-2014
© Author(s) 2014. This work is distributed under
the Creative Commons Attribution 3.0 License.
Research article
01 Oct 2014
A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy
T. W. Tokarek, J. A. Huo, C. A. Odame-Ankrah, D. Hammoud, Y. M. Taha, and H. D. Osthoff Department of Chemistry, University of Calgary, Calgary, Alberta T2N 1N4, Canada
Abstract. 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.

Citation: Tokarek, T. W., Huo, J. A., Odame-Ankrah, C. A., Hammoud, D., Taha, Y. M., and Osthoff, H. D.: A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy, Atmos. Meas. Tech., 7, 3263-3283, https://doi.org/10.5194/amt-7-3263-2014, 2014.
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