Elucidating the chemistry of particulate and chlorinated nitrates in the troposphere through method development, and chamber and field studies

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dc.contributor.advisorOsthoff, Hans D.
dc.contributor.authorGarner, Natasha Michelle
dc.contributor.committeememberGailer, Jürgen G.
dc.contributor.committeememberThurbide, Kevin B.
dc.contributor.committeememberWieser, Michael E.
dc.contributor.committeememberBertram, Timothy H.
dc.date2020-11
dc.date.accessioned2020-09-25T16:45:29Z
dc.date.available2020-09-25T16:45:29Z
dc.date.issued2020-09-22
dc.description.abstractThis thesis explores the chemistry of chlorinated and particulate nitrogen oxides in the troposphere which can impact the budgets of atmospheric oxidants and aerosol. Mixing ratios of nitryl chloride (ClNO2) were measured by chemical ionization mass spectrometry (CIMS) during the ORCA campaign in July 2015 on the west coast of Vancouver Island. Mean ClNO2 mixing ratios were small (< 10 pptv) with a maximum of 46 pptv, in part due to low precursor concentrations, i.e., of nitrogen dioxide (NO2) and ozone, and large nitrate radical sinks, e.g., titration by monoterpenes. Concentrations of ClNO2 were enhanced in air masses with elevated NO2 concentrations that had resided over the ocean, demonstrating the potential of ClNO2 to affect radical budgets in remote environments. The potential loss of ClNO2 by uptake on inorganic and secondary organic aerosol (SOA) was investigated in a newly constructed smog chamber. Uptake probabilities (γ) were determined by box modeling constrained to measured ClNO2 mixing ratios and SMPS derived aerosol surface area. An upper limit of γ< 4x10-4 was determined for (NH4)2SO4 and NH4HSO4 aerosol, but larger values were needed for monoterpene derived SOA, i.e., γ=(8+/-2)x10-4. Uptake of ClNO2 on SOA reduces its lifetime and impact on nitrogen oxide and chlorine budgets downwind of coastal areas where marine and continental air masses combine. A method to quantify NH4NO3 and NaNO3 aerosol by thermal dissociation cavity ring-down spectroscopy (TD-CRDS) was developed. At inlet temperatures of 540 °C and 620 °C, respectively, scatter plots of SMPS volume distribution data and TD-CRDS mixing ratios correlated (r2>0.9) with unity slopes in laboratory experiments. Sample ambient air measurements in Calgary, AB in August 2018 showed the presence of particulate organic nitrates at inlet temperatures < 350 °C (consistent with smog chamber experiments with limonene SOA) and of inorganic nitrate aerosol, demonstrating the potential of TD-CRDS for ambient particulate measurements.en_US
dc.identifier.citationGarner, N. M. (2020). Elucidating the chemistry of particulate and chlorinated nitrates in the troposphere through method development, and chamber and field studies (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.en_US
dc.identifier.doihttp://dx.doi.org/10.11575/PRISM/38234
dc.identifier.urihttp://hdl.handle.net/1880/112574
dc.language.isoengen_US
dc.publisher.facultyScienceen_US
dc.publisher.institutionUniversity of Calgaryen
dc.rightsUniversity of Calgary graduate students retain copyright ownership and moral rights for their thesis. 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.subjectChemistryen_US
dc.subjectAnalyticalen_US
dc.subjectEnvironmentalen_US
dc.subjectAtmospheric Chemistryen_US
dc.subjectNitryl chlorideen_US
dc.subjectClNO2en_US
dc.subjectChemical Ionization Mass Spectrometryen_US
dc.subjectCIMSen_US
dc.subjectCavity Ring-down Spectroscopyen_US
dc.subjectTD-CRDSen_US
dc.subjectParticulate nitratesen_US
dc.subjectSmog chamberen_US
dc.subject.classificationAtmospheric Sciencesen_US
dc.subject.classificationChemistry--Analyticalen_US
dc.subject.classificationEngineering--Chemicalen_US
dc.titleElucidating the chemistry of particulate and chlorinated nitrates in the troposphere through method development, and chamber and field studiesen_US
dc.typedoctoral thesisen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Calgaryen_US
thesis.degree.nameDoctor of Philosophy (PhD)en_US
ucalgary.item.requestcopytrueen_US
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