Composition and Formation Mechanism of Brown Carbon: Identification and Quantification of Phenolic Precursors

Abstract

Light-absorbing organic carbon, collectively known as brown carbon (BrC), significantly influences climate and air quality, particularly in urban environments like Dhaka, Bangladesh. Despite their significance, the contributions and transformation pathways of phenolic compounds – major precursors of brown carbon (BrC) – are still insufficiently understood in the South Asian megacities. This study addresses this gap by investigating the surface morphology of PM2.5, quantifying seven phenolic BrC precursors, and exploring the aqueous-phase formation pathway of nitrophenols at two urban sites (Dhaka South and Dhaka North) from July 2023 to January 2024. Phenolic compounds, including phenol, methylphenols, methoxyphenol, hydroxyphenol, and nitrophenol were identified and quantified using gas chromatography–flame ionization detector (GC-FID). PM2.5 surface morphology and elemental composition were analyzed via Field Emission Scanning Electron Microscopy – Energy Dispersive X-ray Spectroscopy (FESEM-EDX), and functional groups were characterized using Attenuated Total Reflectance – Fourier Transform Infrared Spectroscopy (ATR-FTIR). Results revealed that PM2.5 particles were predominantly spherical or chain-like with carbonaceous elements (C, O, N, S), mineral dust, and trace metals. The dominant functional groups included aromatic conjugate double bond, carbonyl, and nitro group. Aqueous-phase nitration of 2-hydroxyphenol under acidic conditions, analyzed via UV-Vis spectroscopy, demonstrated an alternative nitrophenol formation pathway. Among the detected compounds, 2-hydroxyphenol and 4-nitrophenol showed the highest average concentrations (2.31 ± 1.39 and 2.20 ± 1.21 µg m−3, respectively). Seasonal variations showed elevated nitrophenol levels during winter, especially in Dhaka South (4.54 ± 2.94 µg m−3). These findings highlight the quantification of phenolic precursors and the role of aqueous-phase reactions in BrC formation, providing valuable insights for future atmospheric modeling and air quality management strategies in South Asia.