Asphalt-based materials are abundant and a major nontraditional source of reactive organic compounds in urban areas, but their emissions are essentially absent from inventories. At typical temperature and solar conditions simulating different life cycle stages (i.e., storage, paving, and use), common road and roofing asphalts produced complex mixtures of organic compounds, including hazardous pollutants. Chemically speciated emission factors using high-resolution mass spectrometry reveal considerable oxygen and reduced sulfur content and the predominance of aromatic (~30%) and intermediate/semivolatile organic compounds (~85%), which together produce high overall secondary organic aerosol (SOA) yields. Emissions rose markedly with moderate solar exposure (e.g., 300% for road asphalt) with greater SOA yields and sustained SOA production. On urban scales, annual estimates of asphalt-related SOA precursor emissions exceed those from motor vehicles and substantially increase existing estimates from noncombustion sources. Yet, their emissions and impacts will be concentrated during the hottest, sunniest periods with greater photochemical activity and SOA production.

Abstract. Forest fires are major contributors of reactive gas- and particle-phase organic compounds to the atmosphere. We used offline high-resolution tandem mass spectrometry to perform a molecular-level speciation of gas- and particle-phase compounds sampled via aircraft from an evolving boreal forest fire smoke plume in Saskatchewan, Canada. We observed diverse multifunctional compounds containing oxygen, nitrogen, and sulfur (CHONS), whose structures, formation, and impacts are understudied. The dilution-corrected absolute ion abundance of particle-phase CHONS compounds increased with plume age by a factor of 6.4 over the first 4 h of downwind transport, and their relative contribution to the observed functionalized organic aerosol (OA) mixture increased from 19 % to 40 %. The dilution-corrected absolute ion abundance of particle-phase compounds with sulfide functional groups increased by a factor of 13 with plume age, and their relative contribution to observed OA increased from 4 % to 40 %. Sulfides were present in up to 75 % of CHONS compounds and the increases in sulfides were accompanied by increases in ring-bound nitrogen; both increased together with CHONS prevalence. A complex mixture of intermediate- and semi-volatile gas-phase organic sulfur species was observed in emissions from the fire and depleted downwind, representing potential precursors to particle-phase CHONS compounds. These results demonstrate CHONS formation from nitrogen- and oxygen-containing biomass burning emissions in the presence of reduced sulfur species. In addition, they highlight chemical pathways that may also be relevant in situations with elevated emissions of nitrogen- and sulfur-containing organic compounds from residential biomass burning and fossil fuel use (e.g., coal), respectively.

Abstract. Wildfire impacts on air quality and climate are expected to be exacerbated by climate change with the most pronounced impacts in the boreal biome. Despite the large geographic coverage, there is limited information on boreal forest wildfire emissions, particularly for organic compounds, which are critical inputs for air quality model predictions of downwind impacts. In this study, airborne measurements of 193 compounds from 15 instruments, including 173 non-methane organics compounds (NMOG), were used to provide the most detailed characterization, to date, of boreal forest wildfire emissions. Highly speciated measurements showed a large diversity of chemical classes highlighting the complexity of emissions. Using measurements of the total NMOG carbon (NMOGT), the ΣNMOG was found to be 50 % ± 3 % to 53 % ± 3 % of NMOGT, of which, the intermediate- and semi-volatile organic compounds (I/SVOCs) were estimated to account for 7 % to 10 %. These estimates of I/SVOC emission factors expand the volatility range of NMOG typically reported. Despite extensive speciation, a substantial portion of NMOGT remained unidentified (47 % ± 15 % to 50 % ± 15 %), with expected contributions from more highly-functionalized VOCs and I/SVOCs. The emission factors derived in this study improve wildfire chemical speciation profiles and are especially relevant for air quality modelling of boreal forest wildfires. These aircraft-derived emission estimates were further linked with those derived from satellite observations demonstrating their combined value in assessing variability in modelled emissions. These results contribute to the verification and improvement of models that are essential for reliable predictions of near-source and downwind pollution resulting from boreal forest wildfires.

Abstract. Wildfire impacts on air quality and climate are expected to be exacerbated by climate change with the most pronounced impacts in the boreal biome. Despite the large geographic coverage, there is a lack of information on boreal forest wildfire emissions, particularly for organic compounds, which are critical inputs for air quality model predictions of downwind impacts. In this study, airborne measurements of 250 compounds from 15 instruments, including 228 non-methane organics compounds (NMOG), were used to provide the most detailed characterization, to date, of boreal forest wildfire emissions. Highly speciated measurements showed a large diversity of chemical classes highlighting the complexity of emissions. Using measurements of the total NMOG carbon (NMOGT), the ΣNMOG was found to be 46.2 % of NMOGT, of which, the intermediate- and semi-volatile organic compounds (I/SVOCs) were estimated to account for 7.4 %. These estimates of I/SVOC emission factors expand the volatility range of NMOG typically reported. Despite extensive speciation, a substantial portion of NMOGT remained unidentified (46.4 %), with expected contributions from more highly-functionalized VOCs and I/SVOCs. The emission factors derived in this study improve wildfire chemical speciation profiles and are especially relevant for air quality modelling of boreal forest wildfires. These aircraft-derived emission estimates were further linked with those derived from satellite observations demonstrating their combined value in assessing variability in modelled emissions. These results contribute to the verification and improvement of models that are essential for reliable predictions of near-source and downwind pollution resulting from boreal forest wildfires.

<p>Oil sands are a prominent unconventional source of petroleum. Total organic carbon measurements via an aircraft campaign (Spring-Summer 2018) revealed emissions above Canadian oil sands exceeding reported values by 1900-6300%. The “missing” compounds were predominantly intermediate- and semi-volatile organic compounds, which are prolific precursors to secondary organic aerosol formation. </p> <p>Here we use a novel combination of aircraft-based measurements (including total carbon emissions measurements) and offline analytical instrumentation to characterize the mixtures of organic carbon and their volatility distributions above oil sands facilities. These airborne, real-time observations are supplemented by laboratory experiments identifying substantial, unintended emissions from waste management practices, emphasizing the importance of accurate facility-wide emissions monitoring and total carbon measurements to detect potentially vast missing emissions across sources.</p> <p>Detailed chemical speciation confirms these observations near both surface mining and in-situ facilities were oil sands-derived, with facility-wide emissions around 1% of extracted petroleum—a comparable loss rate to natural gas extraction. Total emissions, spanning extraction through waste processing, were equivalent to total Canadian anthropogenic emissions from all sources. These results demonstrate that the full air quality and environmental impacts of oil sands operations cannot be captured without complete coverage of a wider volatility range of emissions.</p>

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Abstract. Forest fires are major contributors of reactive gas- and particle-phase organic compounds to the atmosphere. We used offline high resolution tandem mass spectrometry to perform a molecular-level speciation of evolving gas- and particle-phase compounds sampled via aircraft from a boreal forest fire in Saskatchewan, Canada. We observed diverse multifunctional compounds containing oxygen, nitrogen, and sulfur (CHONS), whose structure, formation, and impacts are understudied. The abundance of particle-phase CHONS species increased with plume age, from 19 % to 40 % of the relative abundance of observed functionalized OA over the first 4 hours of downwind transport. The relative contribution of particle-phase sulfide functional groups increased with age from 4 % to 40 % of observed OA abundance, and were present in up to 75 % of CHONS compounds. The increases in sulfides were accompanied by increases in ring-bound nitrogen, and both increased together with CHONS prevalence. A complex mixture of intermediate- and semi-volatile gas-phase organic sulfur species was emitted from the fire and depleted downwind, representing potential precursors to particle-phase CHONS compounds. These results demonstrate CHONS formation from nitrogen/oxygen-containing biomass burning emissions in the presence of reduced sulfur species, and highlight chemical pathways that may also be relevant in situations with elevated levels of nitrogen and sulfur emissions from residential biomass burning and fossil fuel use (e.g. coal), respectively.