Articles | Volume 18, issue 6
Atmos. Chem. Phys., 18, 3987–4003, 2018
Atmos. Chem. Phys., 18, 3987–4003, 2018

Research article 22 Mar 2018

Research article | 22 Mar 2018

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

Shunyao Wang1, Jianhuai Ye1, Ronald Soong2, Bing Wu2, Legeng Yu1, André J. Simpson2, and Arthur W. H. Chan1 Shunyao Wang et al.
  • 1Department of Chemical Engineering & Applied Chemistry, University of Toronto, Toronto, Ontario, Canada
  • 2Environmental NMR Centre, Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario, Canada

Abstract. Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomer-rich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance (1H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal–organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

Short summary
Linkages between the chemical composition of PAH-derived SOA and oxidative potential (OP) were investigated under various atmospheric aging processes. Peroxides were found to be an insignificant OP contributor. Oligomerization and heterogeneous ozonolysis may enhance the OP of SOA. Mixing with Cu reduces the OP of PAH-derived SOA. Binding between redox-active Cu(II) and quinone was proved by NMR. Results highlighted the essential role of aerosol chemical composition in its health impact.
Final-revised paper