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Updated: Jun 2, 2026

Characterization, Quantification and Compound-specific Isotopic Analysis of Pyrogenic Carbon Using Benzene Polycarboxylic Acids (BPCA)
Published on: May 16, 2016
Integrated Kinetic and Thermochemical Analysis of Aqueous-Phase Naphthalene Nitration and Its Contribution to Brown
Kristijan Vidović1, Ivana Drventić1,2, Filip Cernatič1
1Department of Analytical Chemistry, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia.
Abstract:
Brown carbon (BrC) is a key light-absorbing component of atmospheric aerosols, yet its sources, particularly those driven by aqueous-phase chemistry, remain poorly constrained, leading to an underestimation of its contribution. Here, we demonstrate efficient nitration and hydroxylation of naphthalene under atmospheric aqueous-phase conditions in the presence of HONO and simulated sunlight, yielding two BrC-active products: 2-nitro-1-naphthol and 1-nitronaphthalene. Contrary to prevailing assumptions, 2-nitro-1-naphthol is the dominant product under atmospherically relevant conditions, whereas 1-nitronaphthalene forms only at elevated solute levels characteristic of aerosol liquid water. The OH-initiated nitration mechanism is elucidated by combining macroscopic kinetic modeling with DFT-based thermochemical calculations, revealing the catalytic role of HONO and the importance of aqueous-phase stabilization of key intermediates. By integrating degradation kinetics (kapp_OH), pathway-specific formation rates (kNOH and kNN), and time-resolved absorbance data, we derive BrC mass absorption coefficients (MACs) of 0.8-20.7 m2 g-1. These values exceed those reported for gas-phase naphthalene nitration, highlighting the importance of aqueous-phase aromatic chemistry for atmospheric radiative forcing.
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