Search

Laboratory and field observations of organic compound emissions reveal a previously unknown source of reactive pollution precursors., 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.

The molecular-level composition and structure of organic aerosol (OA) affect its chemical/physical properties, transformations, and impacts. Here, we use the molecular-level chemical composition of functionalized OA from three diverse field sites to evaluate the effect of molecular-level compositional variability on OA phase state and thermodynamic mixing favorability. For these ambient sites, modeled aerosol phase state ranges from liquid to semisolid. The observed variability in OA composition has some effect on resulting phase state, but other factors like the presence of inorganic ions, aerosol liquid water, and internal versus external mixing with water are determining factors in whether these particles exist as liquids, semisolids, or solids. Organic molecular composition plays a more important role in determining phase state for phase-separated (verus well-mixed) systems. Similarly, despite the observed OA compositional differences, the thermodynamic mixing favorability for OA samples with aerosol liquid water, isoprene oxidation products, or monoterpene oxidation products remains fairly consistent within each campaign. Mixing of filter-sampled OA and isoprene or monoterpene oxidation products is often favorable in both seasons, while mixing with water is generally unfavorable.

The atmospheric evolution of organic compounds encompasses many thousands of compounds with varying volatility, polarity, and water solubility. The molecular-level chemical composition of this mixture plays a major, yet uncertain, role in its transformations and impacts. Here we perform a non-targeted molecular-level intercomparison of functionalized organic aerosol from three diverse field sites and a chamber. Despite similar bulk composition, we report large molecular-level variability between multi-hour organic aerosol samples at each site, with 66 ± 13% of functionalized compounds differing between consecutive samples. Single precursor environmental laboratory chamber experiments and fully chemically-explicit modeling confirm this variability is due to changes in emitted precursors, chemical age, and/or oxidation conditions. These molecular-level results demonstrate greater compositional variability than is typically observed in less-speciated measurements, such as bulk elemental composition, which tend to show less daily variability. These observations should inform future field and laboratory studies, including assessments of the effects of variability on aerosol properties and ultimately the development of strategic organic aerosol parameterizations for air quality and climate models. The detailed molecular-level speciation of organic aerosol is a highly challenging task. Here, the authors show an extensive molecular-level intercomparison of functionalized organic aerosol from three diverse field sites revealing large compositional variability between samples at each field site.