Department of Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 76100, Israel.
Environ Sci Technol. 2022 Apr 19;56(8):4816-4827. doi: 10.1021/acs.est.1c07328. Epub 2022 Apr 6.
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., CHNO, CHNO, CHNO, CHNO) 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.
次生有机气溶胶 (SOA) 通过与紫外线和可见光波长范围内的光相互作用来影响入射太阳辐射。然而,SOA 的化学成分和光学性质之间的关系仍未得到很好的理解。在这项研究中,在线检索了在氮氧化物 (NOx) 存在下 OH 氧化萘产生的 SOA 的复折射率 (RI),在 315-650nm 的波长范围内,并通过在线高分辨率飞行时间质谱仪对 SOA 的体化学成分进行了表征。此外,使用高效液相色谱仪与光电二极管阵列检测器和高分辨率质谱仪确定了棕色碳发色团的分子水平组成。SOA 的 RI 的实部随着 NOx/萘的比例和老化时间的增加而增加,这可能是由于平均极化率的增加和由于碎片化导致的分子量降低。在较高的 NOx 条件下产生的高吸收性硝基芳烃(例如,CHNO、CHNO、CHNO、CHNO)对 SOA 的光吸收有很大贡献。RI 的虚部由于硝基芳烃化合物的形成而随 NOx/VOCs 比例线性增加。随着老化的进行,虚 RI 随 O/C 比增加(斜率=0.024),这主要归因于达到较高的 NOx/VOCs 比,有利于形成光吸收性硝基芳烃。由于反应会使芳环打开,因此与较短的老化时间相比,广泛老化时的光吸收增强并不明显。