4.8 Article

Optical Properties of Secondary Organic Aerosol Produced by Photooxidation of Naphthalene under NOx Condition

Journal

ENVIRONMENTAL SCIENCE & TECHNOLOGY
Volume 56, Issue 8, Pages 4816-4827

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.est.1c07328

Keywords

optical properties; secondary organic aerosol; NOx effect during photooxidation; atmospheric aging; chromophore characterization; chemical composition

Funding

  1. US National Science Foundation (NSF) [AGS-2039985]
  2. US-Israel Binational Science Foundation (BSF) [2020656]

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The chemical composition of secondary organic aerosols (SOAs) and their optical properties were investigated in this study. The results showed that the composition of SOAs affects their ability to absorb solar radiation, with nitroaromatic compounds playing a significant role in the light absorption of SOAs.
Secondary organic aerosols (SOAs) affect incoming solar radiation by interacting with light at ultraviolet and visible wavelength ranges. However, the relationship between the chemical composition and optical properties of SOA is still not well understood. In this study, the complex refractive index (RI) of SOA produced from OH oxidation of naphthalene in the presence of nitrogen oxides (NOx) was retrieved online in the wavelength range of 315-650 nm and the bulk chemical composition of the SOA was characterized by an online high-resolution time-of-flight mass spectrometer. In addition, the molecular-level composition of brown carbon chromophores was determined using high-performance liquid chromatography coupled to a photodiode array detector and a high-resolution mass spectrometer. The real part of the RI of the SOA increases with both the NOx/naphthalene ratio and aging time, likely due to the increased mean polarizability and decreased molecular weight due to fragmentation. Highly absorbing nitroaromatics (e.g., C6H5NO4, C7H7NO4, C(7)H(3)5NO(5), C8H5NO5) produced under higher NOx conditions contribute significantly to the light absorption of the SOA. The imaginary part of the RI linearly increases with the NOx/VOCs ratio due to the formation of nitroaromatic compounds. As a function of aging, the imaginary RI increases with the O/C ratio (slope = 0.024), mainly attributed to the achieved higher NOx/VOCs ratio, which favors the formation of light-absorbing nitroaromatics. The light-absorbing enhancement is not as significant with extensive aging as it is under a lower aging time due to the opening of aromatic rings by reactions.

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