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Contribution of Charge-Transfer Complexes to Absorptivity of Primary Brown Carbon Aerosol

Cite this: ACS Earth Space Chem. 2019, 3, 8, 1393–1401
Publication Date (Web):June 21, 2019
https://doi.org/10.1021/acsearthspacechem.9b00116
Copyright © 2019 American Chemical Society
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Abstract

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Light-absorbing organic aerosol, or brown carbon (BrC), has significant but poorly constrained effects on climate. A large fraction of the absorptivity of ambient BrC is unassigned, and organic charge-transfer (CT) complexes have the potential to contribute to this fraction. Here, the contributions of CT complexes to the absorptivity of laboratory-generated BrC and ambient aerosol material influenced by biomass burning have been investigated, using a wide range of chemical, spectroscopic, and physical analyses. Chemical functionalization experiments are inconclusive about the role of CT complexes, whereas fluorescence spectra exhibit distinct spectral features indicative of individual chromophores. Determinations of the concentration and temperature dependences of absorbance are more conclusive. In particular, for laboratory-generated BrC extracted in either water or methanol, absorbance scaled linearly with orders-of-magnitude changes in concentration, indicating that intermolecular complexes do not contribute to the absorptivity. Furthermore, whereas the absorbance of BrC extracts in dimethyl sulfoxide exhibited a slight temperature dependence, consistent with a 15% contribution from intramolecular CT complexes at 15 °C, the complete temperature independence of absorbance of water-soluble extracts from surrogate and ambient BrC indicates a negligible role for CT complexes. Overall, our results find little evidence for CT complexes in the primary BrC studied, suggesting that they do not contribute significantly to the missing absorptivity of ambient BrC.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsearthspacechem.9b00116.

  • Back trajectories during collection of the first ambient aerosol filter sample (Figure S1). Relative absorption coefficients at 405 and 781 nm of suspended surrogate aerosol particles (Figure S2). Composition of suspended surrogate aerosol particles in terms of f44 and f60 (Figure S3). Mass absorption coefficients (Figure S4), excitation–emission matrices (Figure S5), and fluorescence spectra (Figure S6) of laboratory-generated BrC. 1H NMR spectrum of phenol solution after acetylation (Figure S7). Absorption spectra of BrC in serial dilution experiments (Figure S8). Validation of temperature control using mesitylene and chloranil (Figure S9). Absorption spectra of BrC in solvent dependent experiments (Figure S10) (PDF)

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This article is cited by 18 publications.

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