Quantification of peroxynitric acid and peroxyacyl nitrates using an ethane-based thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer

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dc.contributor.authorTaha, Youssef M.
dc.contributor.authorSaowapon, Matthew T.
dc.contributor.authorAssad, Faisal V.
dc.contributor.authorYe, Connie Z.
dc.contributor.authorChen, Xining
dc.contributor.authorGarner, Natasha M.
dc.contributor.authorOsthoff, Hans D.
dc.date.accessioned2021-06-23T21:28:45Z
dc.date.available2021-06-23T21:28:45Z
dc.date.issued2018-07-17
dc.description.abstractPeroxy and peroxyacyl nitrates (PNs and PANs) are important trace gas constituents of the troposphere which are challenging to quantify by differential thermal dissociation with NO2 detection in polluted (i.e., high-NOx) environments. In this paper, a thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer (TD-PERCA-CRDS) for sensitive and selective quantification of total peroxynitrates (ΣPN  =  ΣRO2NO2) and of total peroxyacyl nitrates (ΣPAN  =  ΣRC(O)O2NO2) is described. The instrument features multiple detection channels to monitor the NO2 background and the ROx ( =  HO2 + RO2 + ΣRO2) radicals generated by TD of ΣPN and/or ΣPAN. Chemical amplification is achieved through the addition of 0.6 ppm NO and 1.6 % C2H6 to the inlet. The instrument's performance was evaluated using peroxynitric acid (PNA) and peroxyacetic or peroxypropionic nitric anhydride (PAN or PPN) as representative examples of ΣPN and ΣPAN, respectively, whose abundances were verified by iodide chemical ionization mass spectrometry (CIMS). The amplification factor or chain length increases with temperature up to 69 ± 5 and decreases with analyte concentration and relative humidity (RH). At inlet temperatures above 120 and 250 °C, respectively, PNA and ΣPAN fully dissociated, though their TD profiles partially overlap. Furthermore, interference from ozone (O3) was observed at temperatures above 150 °C, rationalized by its partial dissociation to O atoms which react with C2H6 to form C2H5 and OH radicals. Quantification of PNA and ΣPAN in laboratory-generated mixtures containing O3 was achieved by simultaneously monitoring the TD-PERCA responses in multiple parallel CRDS channels set to different temperatures in the 60 to 130 °C range. The (1 s, 2σ) limit of detection (LOD) of TD-PERCA-CRDS is 6.8 pptv for PNA and 2.6 pptv for ΣPAN and significantly lower than TD-CRDS without chemical amplification. The feasibility of TD-PERCA-CRDS for ambient air measurements is discussed.en_US
dc.description.grantingagencyNatural Sciences and Engineering Research Council (NSERC)en_US
dc.identifier.citationTaha, Y. M., Saowapon, M. T., Assad, F. V., Ye, C. Z., Chen, X., Garner, N. M., & Osthoff, H. D. (2018). Quantification of peroxynitric acid and peroxyacyl nitrates using an ethane-based thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer. Atmospheric Measurement Techniques, 11(7), 4109–4127. doi:10.5194/amt-11-4109-2018en_US
dc.identifier.doihttp://dx.doi.org/10.5194/amt-11-4109-2018en_US
dc.identifier.grantnumberRGPIN/03849-2016en_US
dc.identifier.urihttp://hdl.handle.net/1880/113532
dc.identifier.urihttps://doi.org/10.11575/PRISM/46063
dc.language.isoengen_US
dc.publisherEuropean Geosciences Unionen_US
dc.publisher.departmentChemistryen_US
dc.publisher.facultyScienceen_US
dc.publisher.hasversionpublishedVersionen_US
dc.publisher.institutionUniversity of Calgaryen_US
dc.rights© Author(s) 2018.en_US
dc.rights.urihttps://creativecommons.org/licenses/by/4.0en_US
dc.titleQuantification of peroxynitric acid and peroxyacyl nitrates using an ethane-based thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometeren_US
dc.typejournal articleen_US
ucalgary.item.requestcopytrueen_US
ucalgary.scholar.levelFacultyen_US
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