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

A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopyAtmospheric Measurement Techniques, 7, 3263-3283, 2014Author(s): T. W. Tokarek, J. A. Huo, C. A. Odame-Ankrah, D. Hammoud, Y. M. Taha, and H. D. OsthoffThe 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.

Atmospheric Measurement Techniques 2014/10/01 - 23:45 Czytaj