Primary and Secondary Organic Aerosol Formation from Asphalt Pavements.

Asphalt is ubiquitous across cities and a source of organic compounds spanning a wide range of volatility and may be an overlooked source of urban organic aerosols. The emission rate and composition depend strongly on temperature, but emissions have been observed at both application temperatures and surface temperatures during warm sunny days. Here we report primary organic aerosol (POA) emissions and secondary organic aerosol (SOA) production from asphalt. We reheated real-world asphalt samples to application-relevant temperatures (∼130 °C) and typical summertime road-surface temperatures (∼55 °C) and then flushed the emitted vapors into an environmental oxidation chamber containing ammonium sulfate seed particles. SOA was then formed following the photo-oxidation of emissions under high-NOx conditions typical of urban atmospheres. We find that POA only forms at application temperature as it does not require further oxidation, whereas SOA forms under both conditions; with the resulting POA and SOA both being semi-volatile. While total OA formation rates were substantially greater under the limited time spent under application conditions, SOA formation from passive asphalt heating presents a potential long-term source, as heating continues for the lifetime of the road surface. This suggests that persistent asphalt solar heating is likely a considerable and continued source of summertime SOA in urban environments.

Limited Secondary Organic Aerosol Production from Acyclic Oxygenated Volatile Chemical Products.

Volatile chemical products (VCPs) have recently been identified as potentially important unconventional sources of secondary organic aerosol (SOA), in part due to the mitigation of conventional emissions such as vehicle exhaust. Here, we report measurements of SOA production in an oxidation flow reactor from a series of common VCPs containing oxygenated functional groups and at least one oxygen within the molecular backbone. These include two oxygenated aromatic species (phenoxyethanol and 1-phenoxy-2-propanol), two esters (butyl butyrate and butyl acetate), and four glycol ethers (carbitol, methyl carbitol, butyl carbitol, and hexyl carbitol). We measured gas- and particle-phase products with a suite of mass spectrometers and particle-sizing instruments. Only the aromatic VCPs produce SOA with substantial yields. For the acyclic VCPs, ether and ester functionality promotes fragmentation and hinders autoxidation, whereas aromatic rings drive SOA formation in spite of the presence of ether groups. Therefore, our results suggest that a potential strategy to reduce urban SOA from VCPs would be to reformulate consumer products to include less oxygenated aromatic compounds.