Enhanced Light Absorption and Elevated Viscosity of Atmospheric Brown Carbon through Evaporation of Volatile Components

Abstract

Samples of brown carbon (BrC) material were collected from smoke emissions originating from wood pyrolysis experiments, serving as a proxy for BrC representative of biomass burning emissions. The acquired samples, referred to as "pyrolysis oil (PO 1 )," underwent subsequent processing by thermal evaporation of their volatile compounds, resulting in a set of three additional samples with volume reduction factors of 1.33, 2, and 3, denoted as PO 1.33 , PO 2 , and PO 3 . The chemical compositions of these PO x samples and their BrC chromophore features were analyzed using a high-performance liquid chromatography instrument coupled with a photodiode array detector and a high-resolution mass spectrometer. The investigation revealed a noteworthy twofold enhancement of BrC light absorption observed for the progression of PO 1 to PO 3 samples, assessed across the spectral range of 300−500 nm. Concurrently, a decrease in the absorption Ångstrom exponent (AAE) from 11 to 7 was observed, indicating a weaker spectral dependence. The relative enhancement of BrC absorption at longer wavelengths was more significant, as exemplified by the increased mass absorption coefficient (MAC) measured at 405 nm from 0.1 to 0.5 m 2 /g. Molecular characterization further supports this darkening trend, manifesting as a depletion of small oxygenated, less absorbing monoaromatic compounds and the retention of relatively large, less polar, more absorbing constituents. Noteworthy alterations of the PO 1 to PO 3 mixtures included a reduction in the saturation vapor pressure of their components and an increase in viscosity. These changes were quantified by the mean values shifting from approximately 1.8 × 10 3 μg/m 3 to 2.3 μg/m 3 and from ∼10 3 Pa•s to ∼10 6 Pa•s, respectively. These results provide quantitative insights into the extent of BrC aerosol darkening during atmospheric aging through nonreactive evaporation. This new understanding will inform the refinement of atmospheric and chemical transport models.