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.accessioned2018-07-31T20:31:16Z
dc.date.available2018-07-31T20:31:16Z
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 0.6ppm 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 (1s, 2σ) limit of detection (LOD) of TD-PERCA-CRDS is 6.8pptv for PNA and 2.6pptv 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 - Discovery Granten_US
dc.description.sponsorshipSponsored by the Open Access Authors Funden_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 Discussions, 1-48. doi:10.5194/amt-2018-113en_US
dc.identifier.doi10.5194/amt-11-4109-2018en_US
dc.identifier.doihttp://dx.doi.org/10.11575/PRISM/35469
dc.identifier.issn1867-8548
dc.identifier.urihttp://hdl.handle.net/1880/107549
dc.language.isoenen_US
dc.publisherCopernicusen_US
dc.publisher.departmentChemistryen_US
dc.publisher.facultyScienceen_US
dc.publisher.institutionUniversity of Calgaryen_US
dc.publisher.policyhttps://www.atmospheric-measurement-techniques.net/about/licence_and_copyright.htmlen_US
dc.rightsUnless otherwise indicated, this material is protected by copyright and has been made available with authorization from the copyright owner. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission.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
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