Field measurements and atmospheric simulation chamber studies of selected biomass burning marker compounds

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O'Sullivan, Niall Patrick
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University College Cork
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Biomass burning is a key contributor to ambient air pollution, which has significant impacts on climate and health. Biomass burning emits both solid particles and gaseous species known as volatile organic compounds (VOCs) which can undergo chemical oxidation reactions in the atmosphere with hydroxyl (OH) and nitrate (NO3) radicals to produce secondary organic aerosols (SOA). While the particulate pollution has been well characterised, information on the VOCs associated with biomass burning is limited. To this end, a Time-of-Flight Chemical Ionisation Mass Spectrometer (ToF-CIMS) was deployed in Cork City, for the first comprehensive field study on the VOCs associated with residential burning of solid fuels (wood, peat, coal) in Ireland. In the field study, a range of phenols and their nitro derivatives were detected during air pollution events caused by residential solid fuel burning. By following the evolution of these biomass burning markers through the night, evidence was found for the atmospheric conversion of phenol compounds to their analogous nitrophenols via gas-phase reaction with NO 3 . Positive matrix factorisation was used to identify six different source categories for the VOCs which included fresh and atmospherically processed emissions from solid fuel burning, as well as oxidized emissions from local and regional background sources such as vehicles and agriculture. A series of simulation chamber studies was also performed on the OH-initiated oxidation of two biomass burning marker compounds, 4-methylcatechol and guaiacol. The ToF-CIMS identified a large range of gas and particle products including polyphenols, nitrophenols, benzoquinones, ring scission species and accretion products, generating new information on the atmospheric degradation pathways. The results confirm the importance of both OH addition and H-atom abstraction reactions in initiating the oxidation processes and interestingly, in the case of guaiacol, loss of the methoxy group to form catechol which also underwent similar degradation pathways. A wide range of highly oxidized and nitro-containing species were identified in the particle phase which experienced further chemical processing, thus providing new insights into the mechanisms for the formation and atmospheric aging of SOA produced from biomass burning.
Atmospheric chemistry , Biomass burning , Molecular characterisation
O'Sullivan, N. P. 2023. Field measurements and atmospheric simulation chamber studies of selected biomass burning marker compounds. PhD Thesis, University College Cork.
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