Radical-Initiated Brown Carbon Formation in Sunlit Carbonyl–Amine–Ammonium Sulfate Mixtures and Aqueous Aerosol Particles

Author(s)

Natalie G. Jimenez, University of San Diego
Kyle D. Sharp, University of San Diego
Tobin Gramyk, University of San Diego
Duncan Z. Ugland, University of San Diego
Matthew-Khoa Tran, University of San Diego
Antonio Rojas, University of San Diego
Michael A. Rafla, University of San Diego
Devoun Stewart, University of San Diego
Melissa M. Galloway, University of San Diego
Peng Lin, Purdue University
Alexander Laskin, Purdue University
Mathieu Cazaunau, Université Paris-Est Créteil (UPEC)
Edouard Pangui, Université Paris-Est Créteil (UPEC)
Jean-François Doussin, Université Paris-Est Créteil (UPEC)
David O. De Haan, University of San DiegoFollow

Document Type

Article

Publication Date

1-6-2022

Journal Title

ACS Earth and Space Chemistry

DOI

https://doi.org/10.1021/acsearthspacechem.1c00395

Version

Pre-print: the initial article submitted to the journal for consideration (prior to peer review)

Disciplines

Chemistry

Abstract

Brown carbon (BrC) formed from glyoxal+ammonium sulfate (AS) and methylglyoxal+AS reactions photobleaches quickly, leading to the assumption that BrC formed overnight by Maillard reactions will be rapidly destroyed at sunrise. Here, we tested this assumption by reacting glyoxal, methylglyoxal, glycolaldehyde, or hydroxyacetone in aqueous mixtures with reduced nitrogen species at pH 4–5 in the dark and in sunlight (>350 nm) for at least 10 h. The absorption of fresh carbonyl+AS mixtures decreased when exposed to sunlight, and no BrC formed, as expected from previous work. However, the addition of amines (either methylamine or glycine) allowed BrC to form in sunlight at comparable rates as in the dark. Hydroxyacetone+amine+AS aqueous mixtures generally browned faster in sunlight than in the dark, especially in the presence of HOOH, indicating a radical-initiated BrC formation mechanism is involved. In experiments with airborne aqueous aerosol containing AS, methylamine, and glyoxal or methylglyoxal, browning was further enhanced, especially in sunlight (>300 nm), forming aerosol with optical properties similar to “very weak” atmospheric BrC. Liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) analysis of aerosol filter extracts indicates that exposure of methylglyoxal+AS aqueous aerosol to methylamine gas, sunlight, and cloud processing increases incorporation of ammonia, methylamine, and photolytic species (e.g., acetyl radicals) into conjugated oligomer products. These results suggest that when amines are present, photolysis of first-generation, “dark reaction” BrC (imines and imidazoles) initiates faster, radical-initiated browning processes that may successfully compete with photobleaching, are enhanced in aqueous aerosol particles relative to bulk liquid solutions, and can produce BrC consistent with atmospheric observations.

Notes

Final published version available at https://doi.org/10.1021/acsearthspacechem.1c00395

Digital USD Citation

Jimenez, Natalie G.; Sharp, Kyle D.; Gramyk, Tobin; Ugland, Duncan Z.; Tran, Matthew-Khoa; Rojas, Antonio; Rafla, Michael A.; Stewart, Devoun; Galloway, Melissa M.; Lin, Peng; Laskin, Alexander; Cazaunau, Mathieu; Pangui, Edouard; Doussin, Jean-François; and De Haan, David O., "Radical-Initiated Brown Carbon Formation in Sunlit Carbonyl–Amine–Ammonium Sulfate Mixtures and Aqueous Aerosol Particles" (2022). Chemistry and Biochemistry: Faculty Scholarship. 41.
https://digital.sandiego.edu/chemistry_facpub/41