Abstract
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.
Highlights
Peroxycarboxylic nitric anhydrides (PANs, referred to as peroxyacyl nitrates) are important trace gas constituents of the troposphere (Roberts, 1990, 2007; Altshuller, 1993)
PANs are formed as byproducts in the same photochemistry between NOx and volatile organic compounds (VOCs) that produces ozone (O3) and photochemical smog; they are good chemical markers of the types of VOCs involved in the O3 formation process (Roberts, 2007)
The linear correlation of PAN-GC peak areas with TDCRDS PN mixing ratios over a wide concentration range (e.g., Fig. 7) affirms that thermal dissociation cavity ringdown spectroscopy (TD-cavity ring-down spectroscopy (CRDS)) can be used as a straightforward and implemented PAN-GC calibration method for PAN and Peroxypropionic nitric anhydride (PPN)
Summary
Peroxycarboxylic nitric anhydrides (PANs, referred to as peroxyacyl nitrates) are important trace gas constituents of the troposphere (Roberts, 1990, 2007; Altshuller, 1993). PANs are formed as byproducts in the same photochemistry between NOx and volatile organic compounds (VOCs) that produces ozone (O3) and photochemical smog; they are good chemical markers of the types of VOCs involved in the O3 formation process (Roberts, 2007).
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