Water/Methanol-Insoluble Brown Carbon Can Dominate Aerosol-Enhanced Light Absorption in Port Cities

Light absorption enhancement (E_abs) of black carbon (BC) is a key factor in global climate models and is impacted by brown carbon (BrC) and the lensing effect of coatings. We conducted an in-depth field study on E_abs for ambient aerosols at a monitoring point in Shanghai, China, by real-time aerosol optical property monitoring and high-performance liquid chromatography/diode array detector/quadrupole-time-of-flight mass spectrometry (HPLC/DAD/Q-ToF-MS) analysis. The results showed E_abs at λ = 530 nm caused by the lensing effect was about 1.39 ± 027, accounting for 18.84% of the total light absorption. In this study, BrC is classified as soluble BrC (soluble in both water and methanol) or insoluble BrC (insoluble in both water and methanol). Soluble BrC accounted for 13.68 ± 11.15% of the total aerosol light absorption. For the first time, we concluded that insoluble BrC can contribute more than 60 and 97% of total aerosol and BrC light absorption in port cities, respectively. The molecular analysis of soluble BrC identified N-containing aromatic compounds (4-nitrophenol, 4-nitrocatechol, methyl nitrophenol, methyl nitrocatechols, and nitro-1-naphthol) commonly observed in biomass burning emissions or biomass burning-impacted atmospheres. A series of components (C₁₆H₂₆O₃S, C₁₇H₂₈O₃S, C₁₈H₃₀O₃S, and C₁₉H₃₂O₃S) were determined to be emissions from nearby cargo ships filled with heavy fuel oil (HFO), which further confirmed that insoluble BrC emitted from cargo ships could be the largest contributor to E_abs. This study confirms the global significance of evaluating HFO used in port cities in climate models. The control measures of cargo ship emission should be considered for the related environmental and health issues in port cities.